TW202108820A - Composition and etching method - Google Patents

Abstract

Provided is a composition that can be used to etch a metal layer, e.g. a copper layer, and that makes it possible to form a fine pattern that has excellent dimensional precision and little cross-sectional narrowing of fine lines while suppressing the generation of a residual film. A composition that is an aqueous solution that contains (A) 0.1-25 mass% of at least one type of component selected from the group that consists of cupric ions and ferric ions, (B) 0.1-30 mass% of chloride ions, (C) 0.01-10 mass% of a compound that is represented by general formula (1) and has a number average molecular weight of 350-1,200, (D) 0.01-10 mass% of at least one type of component selected from the group that consists of unsaturated carboxylic acids and salts and anhydrides thereof, and water.

Description

Composition and etching method

The present invention relates to a composition containing a specific compound and an etching method using it.

Circuit formation methods for printed circuit boards, semiconductor package substrates, etc., are known: the addition method of adding a circuit pattern to the substrate afterwards, and the removal method of forming a circuit pattern by removing unnecessary parts from the metal foil on the substrate (etching method) ). At present, the removal method (etching method) with lower manufacturing cost is generally adopted in the manufacture of printed circuit boards. However, in recent years, with the miniaturization and higher performance of electronic devices, the development and evolution of etching solutions that can form fine patterns with close to rectangular cross-sectional shapes on printed circuit boards has been made.

For example, the microetching agent disclosed in Patent Document 1 contains copper (II) oxide, formic acid, sodium chloride, a polymer, and an acetylene glycol polyoxyethylene adduct. In addition, the etching solution for copper or copper alloy disclosed in Patent Document 2 contains iron (III) chloride, oxalic acid, and ethylenediaminetetrapolyoxyethylene polyoxypropylene. In addition, the microetching agent disclosed in Patent Document 3 contains nitric acid, iron (III) nitrate, and unsaturated carboxylic acid. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] International Publication No. 2013/187537 [Patent Document 2] Japanese Patent Laid-Open No. 2012-107286 [Patent Document 3] Japanese Patent Laid-Open No. 9-241870

(The problem to be solved by the invention)

However, when the etching solution disclosed in the above patent document is used to etch the copper-based layer to form a thin line, the cross section of the thin line will form a necked shape, it is difficult to form a fine pattern with the required dimensional accuracy, and it is likely to be broken. The problem with the residual film caused by the short circuit. The above-mentioned "necked shape" refers to the shape of the cross-sectional shape of the thin wire when the cross-section of the thin wire is observed. The width of the center of the thin wire is narrower than the width of the upper portion of the thin wire and the width of the lower portion of the thin wire.

The advantage is that the present invention provides a composition capable of forming a fine pattern with reduced cross-section neck of fine lines and excellent dimensional accuracy while suppressing the generation of residual film, and can be effectively used for etching of metal layers such as copper-based layers. In addition, the present invention also provides an etching method using the above-mentioned composition. (Technical means to solve the problem)

The inventors of the present invention have conducted intensive studies in order to obtain the above-mentioned composition, and as a result, found that a composition containing specific components can solve the above-mentioned problems, and completed the present invention.

That is, the composition provided by the present invention contains: (A) 0.1-25% by mass of at least one component selected from the group consisting of copper (II) ions and iron (III) ions; (B) chlorine Compound ion 0.1-30% by mass; (C) 0.01-10% by mass of the compound represented by the following general formula (1); (D) At least one selected from the group consisting of unsaturated carboxylic acid, its salt and anhydride Composition: 0.01-10% by mass; and an aqueous solution of water.

(上述一般式(1)中，R¹ 係表示單鍵、或碳原子數1~4之直鏈狀或分支狀烷二基；R² 與R³ 係各自獨立，表示碳原子數1~4之直鏈狀或分支狀烷二基；R⁴ 與R⁵ 係各自獨立，表示氫原子、或碳原子數1~4之直鏈狀或分支狀烷基；n係各自獨立，表示上述一般式(1)所示化合物之數量平均分子量成為350~1,200的數值。)

(In the above general formula (1), R ¹ represents a single bond, or a linear or branched alkanediyl group ^{with 1 to 4 carbon atoms; R 2} and R ³ are independent of each other and represent 1 to 4 carbon atoms The linear or branched alkanediyl group; R ⁴ and R ⁵ are each independent, representing a hydrogen atom, or a linear or branched alkyl group with 1 to 4 carbon atoms; n is each independent, representing the above general formula (1) The number average molecular weight of the compound shown becomes a value of 350 to 1,200.)

Furthermore, the etching method provided by the present invention includes the step of using the above-mentioned composition to perform etching. (Compared with the effect of previous technology)

According to the present invention, it is possible to provide a composition capable of forming a fine pattern with reduced cross-section neck of thin lines and excellent dimensional accuracy while suppressing the generation of residual film, and can be effectively used for etching of metal layers such as copper-based layers. Furthermore, according to the present invention, an etching method using the above-mentioned composition can also be provided.

Hereinafter, an embodiment of the present invention will be described in detail. The composition of one embodiment of the present invention (hereinafter sometimes referred to as "this composition") contains: (A) at least one component selected from the group consisting of copper (II) ions and iron (III) ions (Hereinafter also referred to as "(A) component"); (B) chloride ion (hereinafter also referred to as "(B) component"); (C) compound represented by general formula (1) (hereinafter also referred to as "( C) component"); (D) at least one component selected from the group consisting of unsaturated carboxylic acid, its salt and anhydride (hereinafter also referred to as "(D) component"); and an aqueous solution with water as an essential component.

This composition system is suitable as an etchant composition for etching metal layers such as copper-based layers. Examples of the copper-based layer system include layers containing copper alloys such as silver-copper alloys and aluminum-copper alloys; and copper. Among them, this composition is suitable as an etchant composition for etching a copper-containing copper-based layer.

The term "etching" in this manual refers to the technique of shaping or surface processing using the corrosive effect of chemicals, etc. Specific uses of the etching solution composition formed from the composition include, for example, a remover, a surface smoothing agent, a surface roughening agent, a pattern forming agent, a cleaning solution for a trace component attached to a substrate, and the like. If the above-mentioned etching solution composition is used for the 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 suitable as a pattern forming agent. In addition, since the removal rate of the copper-containing layer is fast, it is also suitable as a remover.

(A) For the component system, copper (II) ions and iron (III) ions may be used alone or in combination. By blending copper (II) compounds, copper (II) ions can be contained in the composition. That is, a copper (II) compound can be used as a supply source of copper (II) ions. In addition, by blending iron (III) compounds, iron (III) ions can be contained in the composition. That is, an iron (III) compound can be used as a supply source of iron (III) ions.

Examples of the copper (II) compound system include copper (II) chloride, copper (II) bromide, copper sulfate (II), and copper hydroxide (II). Examples of iron (III) compound systems include iron (III) chloride, iron (III) bromide, iron (III) iodide, iron (III) sulfate, iron (III) nitrate, and iron (III) acetate, etc. . These compounds can be used individually by 1 type or in combination of 2 or more types. Among these compounds, copper(II) chloride and iron(III) chloride are preferred, and copper(II) chloride is more preferred.

The concentration of the component (A) in the composition is 0.1 to 25% by mass, preferably 0.5 to 23% by mass, and more preferably 1 to 20% by mass. For example, when the composition is used as an etching solution composition, the concentration of the component (A) can be adjusted appropriately according to the thickness, width, etc. of the object to be etched. The concentration of the component (A) refers to the concentration of copper (II) ions or the concentration of iron (III) ions when copper (II) ions or iron (III) ions are used alone. In addition, when copper (II) ions and iron (III) ions are used in combination (mixed), it refers to the total of the concentration of copper (II) ions and the concentration of iron (III) ions. For example, when copper (II) chloride contains 10% by mass, the concentration of component (A) is about 4.7% by mass. In addition, when copper (II) chloride contains 10% by mass and iron (III) chloride contains 10% by mass, the concentration of component (A) is approximately 8.2% by mass. When copper (II) ions and iron (III) ions are used in combination (mixed), the concentration of iron (III) ions is preferably less than 5% by mass.

(B) The supply source of the component (chloride ion) can use, for example: hydrogen chloride, sodium chloride, calcium chloride, potassium chloride, barium chloride, ammonium chloride, iron (III) chloride, copper chloride ( II), manganese chloride (II), cobalt chloride (II), cerium chloride (III), zinc chloride (II), etc. These (B) component supply sources can be used individually by 1 type or in combination of 2 or more types. Among them, when the present composition is used as an etching solution composition, hydrogen chloride, iron (III) chloride, and copper (II) chloride are preferred for reasons such as easy control of the etching rate and easy control of the shape of the wiring pattern. More preferably, hydrogen chloride.

The concentration of the component (B) in the composition is 0.1 to 30% by mass, preferably 0.5 to 28% by mass, and more preferably 1 to 25% by mass. For example, when the present composition is used as an etchant composition, the concentration of the component (B) can be adjusted appropriately according to the thickness, width, etc. of the object to be etched. If the concentration of the component (B) is less than 0.1% by mass, when the composition is used as an etching solution composition, the etching rate may be insufficient. On the other hand, if the concentration of the component (B) exceeds 30% by mass, defects such as corrosion of the device components are likely to occur.

In this composition, the mass ratio of (B) component relative to (A) component is preferably (B)/(A)=0.5~2, more preferably 0.6~1.8, particularly preferably 0.7~1.7, most preferably It is 0.8~1.7. If the value of (B)/(A) is 2 or less, when this composition is used as an etching solution composition, a fine wiring pattern with excellent dimensional accuracy can be easily formed. On the other hand, if the value of (B)/(A) is 0.5 or more, the etching rate can be easily increased when the composition is used as an etching solution composition.

(C) The component is a compound having a number average molecular weight of 350 to 1,200 represented by the following general formula (1). This (C) component can be used individually by 1 type or in combination of 2 or more types.

(一般式(1)中，R¹ 係表示單鍵、或碳原子數1~4之直鏈狀或分支狀烷二基；R² 及R³ 係各自獨立，表示碳原子數1~4之直鏈狀或分支狀烷二基；R⁴ 及R⁵ 係各自獨立，表示氫原子、或碳原子數1~4之直鏈狀或分支狀烷基；n係各自獨立，表示上述一般式(1)所示化合物之數量平均分子量成為350~1,200的數值。)

(In general formula (1), R ¹ represents a single bond, or a linear or branched alkanediyl group ^{with 1 to 4 carbon atoms; R 2} and R ³ are independent of each other and represent a single bond with 1 to 4 carbon atoms. Linear or branched alkanediyl group; R ⁴ and R ⁵ are each independent and represent a hydrogen atom or a linear or branched alkyl group with 1 to 4 carbon atoms; n is each independent and represents the above general formula ( 1) The number average molecular weight of the compound shown becomes a value of 350 to 1,200.)

In general formula (1), R ¹ represents a single bond, or a linear or branched alkanediyl group having 1 to 4 carbon atoms. In addition, R ² and R ³ are independent of each other, and represent a linear or branched alkanediyl group having 1 to 4 carbon atoms. R ¹ , R ² , and R ^{3 are} straight-chain or branched alkanediyl groups with 1 to 4 carbon atoms, and examples include: methylene, ethylene, propylene, and methylethylene , Butylene, ethyl ethylene, 1-methyl propylene, and 2-methyl propylene. The alkanediyl system may be only one type or a combination of two or more types. When the present composition is used as an etching solution composition, from the viewpoints of easy control of the etching rate and easy suppression of side etching, R ^{1 is} preferably an ethylene group, and R ² and R ^{3 are} preferably a methyl ethylene group.

In general formula (1), R ⁴ and R ⁵ are independent of each other and represent a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms. The straight-chain or branched alkyl groups with 1 to 4 carbon atoms represented by R ⁴ and R ⁵ include, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and second Butyl, tertiary butyl. When the present composition is used as an etching solution composition, from the viewpoints of easy control of the etching rate and easy suppression of side etching, R ⁴ and R ^{5 are} preferably hydrogen atoms.

In the general formula (1), the n systems are independent of each other, and represent a value at which the number average molecular weight of the compound represented by the general formula (1) becomes 350 to 1,200. When the present composition is used as an etchant composition, from the viewpoint of easy control of the etching rate and easy suppression of side etching, the coefficient average molecular weight of n is preferably a value of 450 to 1,050, and more preferably a value of 550 to 950. In addition, the above-mentioned number average molecular weight can be determined by using GPC (Gel Permeation Chromatography Analyzer) based on polystyrene.

Preferred specific examples of the compound represented by the general formula (1) include, for example, the compounds represented by the following formulas No. 1 to No. 36. In the following formulas No. 1 to No. 36, "Me" represents a methyl group, "Et" represents an ethyl group, and "iPr" represents an isopropyl group. In addition, n systems are independent of each other, and indicate that the number average molecular weight of the compounds shown in No. 1 to No. 36 becomes a value of 350 to 1,200.

The method for producing the component (C) is not particularly limited, and it can be produced by applying a well-known reaction. For example, the compound represented by the above formula No. 17 can be produced by using ethylenediamine and propylene oxide as raw materials and following the reaction represented by the following formula (3). "Me" in the following formula (3) represents a methyl group.

The concentration of the component (C) in the composition is 0.01 to 10% by mass, preferably 0.05 to 8% by mass, and more preferably 0.1 to 5% by mass. If the concentration of the component (C) is less than 0.01% by mass, the desired effect due to the compounding of the component (C) may not be obtained. On the other hand, if the concentration of the component (C) exceeds 10% by mass, when the present composition is used as an etching solution composition, the etching rate is likely to decrease. In addition, at the interface between a metal layer such as a copper-based layer and the photoresist, the etching solution composition may easily penetrate, and pattern shape defects may easily occur.

In this composition, the mass ratio of (C) component to the total of (A) component and (B) component is preferably (C)/((A)+(B))=0.005~0.2, more preferably 0.01~0.15, especially good range 0.015~0.1. If the value of (C)/((A)+(B)) is 0.2 or less, when this composition is used as an etching solution composition, it is easy to increase the etching rate. On the other hand, if the value of (C)/((A)+(B)) exceeds 0.005, the desired effect caused by the blending of the (C) component can be easily obtained.

The (D) component used in this composition is not particularly limited, and one or two or more of known general unsaturated carboxylic acids, their salts, and anhydrides can be used. In this specification, unsaturated carboxylic acid also includes aromatic carboxylic acid. Examples of unsaturated carboxylic acids include phthalic acid, fumaric acid, acrylic acid, methacrylic acid, maleic acid, acetylene dicarboxylic acid, pyromellitic acid, dipicolinic acid, 3,5-dicarboxylic acid, Hydroxybenzoic acid, gallic acid, etc. In addition, these salts and these anhydrides can be exemplified as salts of unsaturated carboxylic acids and anhydrides of unsaturated carboxylic acids, respectively. Examples of the cation constituting the salt of the unsaturated carboxylic acid include sodium ion, potassium ion, calcium ion, and ammonium ion.

Among the above-mentioned specific examples of component (D), from the viewpoint that when the composition is used as an etching solution composition, the necking of the cross section of the thin wire obtained is small, phthalic acid, fumaric acid, and acetylene dicarboxylic acid are preferred. Acid, pyromellitic acid, dipicolinic acid, 3,5-dihydroxybenzoic acid, and gallic acid, and their salts and anhydrides. Among these, more preferred are monopotassium acetylene dicarboxylate, potassium hydrogen phthalate, 3,5-dihydroxybenzoic acid, and gallic acid, and particularly preferred is monopotassium acetylene dicarboxylate.

The concentration of the component (D) in the composition is 0.01 to 10% by mass, preferably 0.03 to 5% by mass, and more preferably 0.05 to 1% by mass. If the concentration of (D) component is less than 0.01% by mass, even if the composition is used as an etching solution composition, it is not easy to form a pattern with a narrow neck of the thin line. If the concentration of (D) component exceeds 10% by mass, it is not easy to increase the blending (D) The effect caused by the ingredient.

In this composition, the mass ratio of (D) component to the total of (A) component, (B) component and (C) component is preferably (D)/((A)+(B)+(C) )=0.0005~0.1, more preferably 0.001~0.05, especially good 0.003~0.04, best 0.005~0.03. If the value of (D)/((A)+(B)+(C)) is below 0.1, component (D) can be easily dissolved. On the other hand, if the value of (D)/((A)+(B)+(C)) is above 0.0005, the desired effect caused by the blending of (D) component can be easily obtained.

This composition is an aqueous solution containing water as an essential component, and each component is dissolved in water. Water system can be used: ion exchange water, pure water, ultrapure water and other water from which ionic substances and impurities have been removed. The water content in this composition may be as long as 50 to 99% by mass.

This composition system can be suitably used as an etchant (etching solution) for etching metal layers such as copper-based layers, additives for electroless plating solutions, additives for metal electrolytic refining, pesticides, and insecticides. Among them, it is suitable as an etchant composition for etching a metal layer.

When this composition is an etching solution composition, in the etching solution composition, components other than (A) component, (B) component, (C) component, (D) component, and water are not damaged And within the scope of the effects of the present invention, well-known additives and solvents can also be formulated. Examples of additives include: stabilizers of the etching solution composition, solubilizers of each component, pH adjusters, specific gravity adjusters, viscosity adjusters, wettability improvers, chelating agents, oxidizing agents, reducing agents, and interfacial activity剂 etc. The concentration of these additives may be within the range of 0.001-50% by mass, preferably within the range of 0.001-49% by mass, and more preferably within the range of 0.001-40% by mass.

等氫氧化四級銨類；乙胺、二乙胺、三乙胺、羥乙胺等有機胺類；碳酸銨；碳酸氫銨；氨等。該等pH調節劑係可單獨使用1種、或組合使用2種以上。pH調節劑含有量係只要蝕刻液組成物的pH能成為所需pH的量便可。Examples of pH adjusting agents include: inorganic acids 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; hydroxides Alkaline earth metals such as calcium, strontium hydroxide, and barium hydroxide; carbonates of alkali metals such as lithium carbonate, sodium carbonate and potassium carbonate; bicarbonates of alkali metals such as sodium bicarbonate and potassium bicarbonate; hydrogen Tetramethylammonium Oxide, Bile

And other quaternary ammonium hydroxides; organic amines such as ethylamine, diethylamine, triethylamine, and hydroxylethylamine; ammonium carbonate; ammonium bicarbonate; ammonia, etc. These pH adjusters can be used individually by 1 type or in combination of 2 or more types. The content of the pH adjuster may be as long as the pH of the etching solution composition becomes the required pH.

Examples of chelating agents include: ethylenediaminetetraacetic acid, ethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, tetraethylenepentamine heptaacetic acid, pentaethylenehexamine octaacetic acid, nitrotriacetic acid , And these alkali metal (preferably sodium) salts and other amino carboxylic acid chelating agents; hydroxyethylene diphosphonic acid, nitrogen trimethylene phosphonic acid, phosphinyl butane tricarboxylic acid, and the Phosphonic acid chelating agents such as alkali metal (preferably sodium) salts; oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, malic acid, tartaric acid, citric acid, etc. Anhydrides, and these alkali metal (preferably sodium) salts, etc., dihydric or higher carboxylic acid compounds, and dehydrated monohydric or dianhydrides of dihydric or higher carboxylic acid compounds. The concentration of the chelating agent in the etching solution composition is generally in the range of 0.01-40% by mass, preferably in the range of 0.05-30% by mass.

啉鎓鹽、聚氧乙烯烷基(烯基)胺、烷基(烯基)胺鹽、多胺脂肪酸衍生物、戊醇脂肪酸衍生物、氯化苄烷銨、氯化苯索寧(benzethonium chloride)等。兩性界面活性劑係可舉例如：羧基甜菜

、磺基甜菜

、磷酸酯甜菜

、醯胺胺基酸、咪唑鎓甜菜

系界面活性劑等。蝕刻液組成物中的界面活性劑濃度，一般係0.001~10質量%的範圍。As the surfactant system, cationic surfactants and amphoteric surfactants can be used. Examples of cationic surfactants include alkyl (alkenyl) trimethyl ammonium salt, dialkyl (alkenyl) dimethyl ammonium salt, alkyl (alkenyl) pyridinium salt, and alkyl (alkenyl) dimethyl ammonium salt. Benzylammonium salt, alkyl (alkenyl) isoquinolinium salt, dialkyl (alkenyl)

Phyrinium salts, polyoxyethylene alkyl (alkenyl) amines, alkyl (alkenyl) amine salts, polyamine fatty acid derivatives, pentanol fatty acid derivatives, benzalkonium chloride, benzethonium chloride )Wait. Amphoteric surfactants include, for example: carboxyl beet

Sulfobeet

Phosphate beet

, Amino acid, imidazolium beet

Department of surfactants, etc. The concentration of the surfactant in the etching solution composition is generally in the range of 0.001 to 10% by mass.

As the solvent system, alcohol-based solvents, ketone-based solvents, ether-based solvents, and the like can be used. Examples of the alcohol-based solvent system include methanol, ethanol, diethylene glycol, isopropanol, and 2-ethylhexanol. Examples of the ketone solvent system include methyl acetate, ethyl acetate, and propyl acetate. Examples of the ether-based solvent system include tetrahydrofuran, methyl serosol, and the like.

An etching method according to an embodiment of the present invention includes a step of performing etching using the above-mentioned present composition (etching solution composition). In addition to using the above-mentioned etching solution composition, the etching method can also adopt the steps of a well-known general etching method. The etched material is in the metal layer, especially the copper layer. Examples of the copper-based layer system include copper alloys such as silver-copper alloys and aluminum-copper alloys; and layers containing copper. Among them, copper is particularly good. As a specific etching method, for example, a dipping method, a spray method, etc. can be used. Regarding the etching conditions, as long as the composition of the etching solution composition used and the etching method are adjusted appropriately. In addition, various well-known methods such as batch type, flow type, and automatic control type using the oxidation-reduction potential, specific gravity, and acid concentration of the etching solution may also be used.

The etching conditions are not particularly limited, and can be set arbitrarily according to the shape and film thickness of the object to be etched. For example, it is preferable to spray the etching solution composition at 0.01 to 0.2 MPa, and more preferably to spray at 0.01 to 0.1 MPa. In addition, the etching temperature is preferably 10-50°C, more preferably 20-50°C. Since the temperature of the etching solution composition rises due to the heat of reaction, if necessary, the temperature can be controlled by well-known means so as to be maintained within the above-mentioned temperature range. The etching time may be set to a time that the object to be etched can be sufficiently etched. For example, for an object to be etched with a film thickness of about 1 μm, a line width of about 10 μm, and an opening of about 100 μm, when etching is performed in the above-mentioned temperature range, the etching time may be set to about 10 to 300 seconds.

According to the etching method using the above-mentioned etching solution composition, it is possible to form a fine pattern with a reduced cross-section neck of the thin line while suppressing the generation of residual film. Therefore, in addition to printed circuit boards, it is also applicable to the removal method for packaging substrates, COF, and TAB applications that require fine pitch.

As described in detail above, the following configuration can be adopted for the above-mentioned embodiment. [1] A composition containing: (A) 0.1-25% by mass of at least one component selected from the group consisting of copper (II) ions and iron (III) ions; (B) 0.1-25% by mass of chloride ions 30% by mass; (C) 0.01-10% by mass of the compound represented by the general formula (1); (D) at least one component selected from the group consisting of unsaturated carboxylic acid, its salt and anhydride, 0.01-10% by mass %; and an aqueous solution of water. [2] The composition as described in the above [1], wherein the mass ratio of the (B) component to the (A) component is (B)/(A)=0.5-2. [3] The composition according to the above [1] or [2], wherein the mass ratio of the (C) component to the total of the (A) component and the (B) component is (C)/( (A)+(B))=0.005~0.2. [4] The composition according to any one of the above [1] to [3], wherein the (D) component is relative to the total of the (A) component, the (B) component, and the (C) component The mass ratio of is (D)/((A)+(B)+(C))=0.0005~0.1. [5] The composition as described in any one of [1] to [4] above is an etchant composition used for etching a metal layer. [6] The composition according to [5] above, wherein the metal layer is a copper-based layer. [7] An etching method including a step of performing etching using the composition described in any one of [1] to [6] above. [Example]

Hereinafter, examples and comparative examples are used to describe the present invention in detail, but the present invention is not limited by these.

Table 1 shows the number average molecular weight of the (C) component and its comparative components used in the examples and comparative examples. In Table 1, c-1, c-2 and c-3 of the component (C) are all the compounds represented by the above formula No.17, and n in the above formula No.17 is the number of the compounds represented by the above formula No.17 The compound whose average molecular weight becomes the value shown in Table 1. In addition, c-4 of the comparative component of the (C) component is a value other than the value shown in Table 1 except that n in the above formula No.17 is the number average molecular weight of the compound shown in the above formula No.17, and the rest are all It is a compound represented by the same chemical formula as the above formula No.17.

[Table 1] (C) Ingredients or comparative ingredients Number average molecular weight c-1 850 c-2 650 c-3 1,100 c-4 1,500

The component (D) used in the examples and comparative examples is shown below:

d-1: Monopotassium acetylene dicarboxylate d-2: Potassium hydrogen phthalate d-3: pyromellitic acid d-4: 2,6-pyridinedicarboxylic acid d-5: Sodium hydrogen fumarate d-6: Gallic acid d-10: 3,5-dihydroxybenzoic acid

In addition, the comparative component system of (D) component prepares the following d-7~d-9: d-7: Sodium acetate d-8: Potassium Sodium Tartrate d-9: Tartaric acid

<Example 1 (Examples 1-1 to 1-14) and Comparative Example 1 (Comparative Examples 1-1 to 1-6)> According to the composition shown in Table 2, copper (II) chloride, hydrogen chloride, (C) component or its comparative component, (D) component or its comparative component, and water were mixed to obtain etching solution composition No. 1~20. In addition, the remainder of the composition of the etching solution composition shown in Table 2 is water.

[Table 2] Etching solution composition No. (A) component copper (II) ion mass% (B) Component chloride ion mass% (C) Ingredient type/mass% (D) Ingredient type/mass% Example 1-1 1 12 15 c-1/0.5 c-2/1.5 d-1/0.3 Example 1-2 2 12 15 c-1/1.0 c-2/1.0 d-1/0.2 Example 1-3 3 12 15 c-1/1.0 d-1/0.1 Example 1-4 4 12 15 c-1/1.0 d-1/0.2 Example 1-5 5 12 15 c-1/1.0 d-1/0.3 Example 1-6 6 12 15 c-2/1.0 d-1/0.2 Example 1-7 7 12 15 c-3/1.0 d-1/0.3 Example 1-8 8 12 15 c-1/1.0 d-2/0.3 Example 1-9 9 9 15 c-2/1.0 d-2/0.2 Example 1-10 10 9 12 c-1/1.0 d-3/0.2 Example 1-11 11 12 15 c-1/0.5 d-4/0.2 Example 1-12 12 12 15 c-1/1.0 d-5/0.5 Example 1-13 13 12 15 c-1/1.0 d-6/0.2 Example 1-14 14 12 15 c-1/1.0 d-10/0.1 Comparative example 1-1 15 12 15 c-1/0.5 c-2/1.5 d-7/0.3 Comparative example 1-2 16 12 15 c-1/1.0 d-8/0.3 Comparative example 1-3 17 12 15 c-1/1.0 d-9/0.3 Comparative example 1-4 18 12 15 c-1/1.0 - Comparative example 1-5 19 12 15 c-4/1.0 d-1/0.3 Comparative example 1-6 20 12 15 - d-1/0.3

<Example 2 (Examples 2-1 to 2-14) and Comparative Example 2 (Comparative Examples 2-1 to 2-6)> Prepare a base in which a copper foil with a thickness of 8 μm is laminated on a polyimide resin base. A photoresist having a pattern with a line width of 11 μm and an opening of 5 μm was formed on the copper foil of the base to prepare a test substrate. For the prepared test substrate, using the prepared etching solution composition, under the conditions of a processing temperature of 45° C. and a processing pressure of 0.05 MPa, wet etching with a spray for an appropriate etching time (60 to 120 seconds) was performed. The "proper etching time" refers to the time calculated from the etching rate until the width of the lower part of the thin line in the cross section of the thin line becomes 8 μm. Then, the photoresist pattern is removed using a peeling liquid to form a pattern (thin line).

＜Evaluation＞ Use a laser microscope to confirm the presence of thin lines and the presence or absence of residual film. In addition, a focused ion beam processing observation device (JIB-4000, manufactured by JEOL Ltd.) was used to process the thin wire cross section, and then the thin wire cross section was observed with a scanning electron microscope (SEM). Then, the measurement of the width of the thin line is performed from the SEM image of the cross section of the thin line. Specifically, referring to FIG. 1 schematically showing a cross-sectional view of a test substrate after etching, the width (width above the thin line) 4 on the side of the photoresist 2 of the cross-section of the etched copper foil 1 is measured. In addition, the width 5 of the center portion of the thin wire narrowed from the width 4 of the upper portion of the thin wire and the width (lower portion of the thin wire) 6 of the cross section of the etched copper foil 1 on the resin base 3 side due to necking was measured. The evaluation results and measurement results of (1) to (5) shown below are shown in Table 3. In addition, there is no residual film (remaining etched part), which means that disconnection and short-circuit are unlikely to occur. In addition, the smaller the necking width is, the closer the thin line is to the rectangular cross-sectional shape.

(1) Whether there are thin lines formed If there is a thin line, it is rated as "++", and if there is no thin line, it is rated as "-". (2) Whether there is residual film The case with no residual film was rated as "++", and the case with residual film was rated as "-". (3) Upper width of thin line Obtain the value measured as described above. The unit is "μm". (4) Width of the center of the thin line Obtain the value measured as described above. The unit is "μm". (5) Neck width It is calculated by the following formula. The unit is "μm". Among them, when there is no thin line formation, since the width of the upper part of the thin line and the width of the center part of the thin line cannot be measured, it is recorded as "unmeasurable". "Neck width" = "Measured value of the width of the upper part of the thin line"-"Measured value of the width of the central part of the thin line"

[table 3] Etching solution composition No. Processing time (seconds) Evaluation item (1) (2) (3) (4) (5) Example 2-1 1 80 ++ ++ 5.8 5.4 0.4 Example 2-2 2 85 ++ ++ 5.7 5.2 0.5 Example 2-3 3 90 ++ ++ 5.9 5.3 0.6 Example 2-4 4 90 ++ ++ 6.0 5.7 0.3 Example 2-5 5 95 ++ ++ 6.1 5.4 0.7 Example 2-6 6 65 ++ ++ 5.5 4.7 0.8 Example 2-7 7 110 ++ ++ 5.7 4.8 0.9 Example 2-8 8 70 ++ ++ 6.1 4.9 1.2 Example 2-9 9 75 ++ ++ 5.8 4.5 1.3 Example 2-10 10 90 ++ ++ 5.5 3.8 1.7 Example 2-11 11 70 ++ ++ 5.8 4.0 1.8 Example 2-12 12 90 ++ ++ 6.1 4.2 1.9 Example 2-13 13 85 ++ ++ 6.2 5.2 1.0 Example 2-14 14 75 ++ ++ 5.8 4.9 0.9 Comparative example 2-1 15 80 ++ ++ 5.8 3.1 2.7 Comparative example 2-2 16 70 ++ ++ 5.7 2.9 2.8 Comparative example 2-3 17 75 ++ ++ 5.6 2.7 2.9 Comparative example 2-4 18 70 ++ ++ 5.1 2.6 2.5 Comparative example 2-5 19 120 ++ ++ 5.5 3.0 2.5 Comparative example 2-6 20 60 －－ －－ Unable to determine Unable to determine Unable to determine

As shown in Table 3, the necking width of Examples 2-1 to 2-14 was less than 2.0 μm, and it was found that a pattern with a small necking width can be formed while suppressing the generation of residual film. In particular, the necking widths of Examples 2-1 to 2-9, 2-13, and 2-14 are less than 1.5 μm. It is known that the necking width can be even greater while suppressing the generation of residual film. Small patterns. In particular, the necking width of Examples 2-1 to 2-7 and Example 2-14 was less than 1.0 μm, and it was found that patterns with extremely small necking widths can be formed while suppressing the generation of residual film. On the other hand, in Comparative Examples 2-1 to 2-5, the necking width was 2.5 μm or more, and it was found that a pattern with a large necking width was formed. In addition, in Comparative Example 2-6, no pattern was formed. From the above results, according to the present embodiment, it is possible to provide an etching composition and an etching method capable of forming a residual film that is less likely to cause disconnection and short-circuit, neck reduction, and a fine pattern with required dimensional accuracy.

1: Copper foil 2: photoresist 3: resin matrix 4: The upper width of the thin line 5: Width of the center of the thin line 6: Width of lower part of thin line 7: photoresist line width

Fig. 1 schematically shows a cross-sectional view of a test substrate after etching.

Claims (7)

A composition containing: (A) 0.1-25% by mass of at least one component selected from the group consisting of copper (II) ions and iron (III) ions; (B) 0.1-30% by mass of chloride ions (C) 0.01-10% by mass of the compound represented by the following general formula (1); (D) 0.01-10% by mass of at least one component selected from the group consisting of unsaturated carboxylic acids, their salts and anhydrides; And an aqueous solution of water;

(In the above general formula (1), R ¹ represents a single bond, or a linear or branched alkanediyl group ^{with 1 to 4 carbon atoms; R 2} and R ³ are independent of each other and represent 1 to 4 carbon atoms The linear or branched alkanediyl group; R ⁴ and R ⁵ are each independent, representing a hydrogen atom, or a linear or branched alkyl group with 1 to 4 carbon atoms; n is each independent, representing the above general formula (1) The number average molecular weight of the compound shown becomes a value of 350 to 1,200). Such as the composition of claim 1, wherein the mass ratio of the above-mentioned (B) component to the above-mentioned (A) component is (B)/(A)=0.5~2. The composition of claim 1, wherein the mass ratio of the above-mentioned (C) component to the total of the above-mentioned (A) component and the above-mentioned (B) component is (C)/((A)+(B))=0.005 ~0.2. The composition of claim 1, wherein the mass ratio of the above-mentioned (D) component to the total of the above-mentioned (A) component, the above-mentioned (B) component, and the above-mentioned (C) component is (D)/((A)+ (B)+(C))=0.0005~0.1. The composition of any one of claims 1 to 4 is an etchant composition used for etching a metal layer. The composition of claim 5, wherein the metal layer is a copper-based layer. An etching method includes: using the composition of any one of claims 1 to 6 to perform etching.

Images