WO2017086758A1 - Composition for etching copper, and hydrogen peroxide-based composition for etching metal - Google Patents

Abstract

The present invention relates to: a composition for etching copper; and a hydrogen peroxide-based composition for etching metal and, more specifically, to: a composition for etching copper, capable of inhibiting the generation of a copper precipitate from the etching composition by increasing the stability of a chelate bond formed between copper and organic matter; and a hydrogen peroxide-based composition for etching metal, capable of preventing the decomposition of hydrogen peroxide and the degeneration of the other components within the hydrogen peroxide-based composition for etching metal.

Description

Copper Etching Compositions and Hydrogen Peroxide-based Metal Etching Compositions

The present invention relates to a composition for etching copper or a composition for hydrogen peroxide-based metal etching, and more particularly, a composition for etching copper, which can suppress the generation of copper precipitates from the composition for etching by increasing the stability of the chelate bond formed between copper and the organic material. The present invention relates to a hydrogen peroxide-based metal etching composition capable of preventing decomposition of hydrogen peroxide in a composition and denaturation of other components.

BACKGROUND ART Semiconductor devices, display devices, printed circuit boards, IC cards and the like generally form metal thin film elements, electrode wiring elements, and the like by patterning a metal thin film or the like on a substrate.

As a processing technique for patterning such a metal thin film into a fine structure such as wiring, a wet etching patterned by etching with chemicals using a photoresist pattern formed on the metal thin film surface by photolithography as a mask. And dry etching such as ion etching or plasma etching.

Among them, the wet etching method is economically advantageous because it does not require an expensive device, unlike the dry etching method, and uses a relatively inexpensive chemical. In addition, there is an advantage that it is possible to provide a uniform etching even in a large area and / or a substrate of various shapes. Due to the above advantages, wet etching is mainly used as a method of manufacturing a thin film pattern at present.

Recently, as a material used for metal thin film elements, electrode wirings, and other elements used in semiconductors and liquid crystal displays, and the like, copper, titanium, molybdenum, or alloys thereof having low electrical resistance and easy processability into thin film patterns Metals are preferred.

For the wet etching described above, a metal etchant (or a composition for metal etching) is essential. Most metal etchant has a hydrogen peroxide-based etchant having excellent cost and performance.

Hydrogen peroxide-based etchant is prepared by mixing chelating agents and other additives with hydrogen peroxide. When excess copper is dissolved into the etchant as the copper is etched, unstable hydrogen peroxide is decomposed and the performance of the etchant is often found. It became.

In addition, as the hydrogen peroxide is decomposed, some of the copper dissolved in the etchant has a problem of precipitation in the form of precipitates in the form of solids or sludges.

Such a copper precipitate may cause problems such as impairing the performance of the hydrogen peroxide-based etchant in the chamber where copper is etched or being precipitated in a pipe or the like and inhibiting the flow of liquid.

Therefore, in the related art, in order to prevent excessive copper dissolving to decompose hydrogen peroxide and to generate copper precipitate due to decomposition of hydrogen peroxide, the replacement cycle with a new etchant was short.

Hydrogen peroxide-based etchant is another problem, and the quality characteristics of the etching result are changed by chemical action between various components contained in the etchant, and particularly over time (EPD change, residue occurrence, stability of etchant, etc.). Will make a big difference.

Therefore, it is essential to precisely control the type and ratio when combining the components having a specific functional group, which requires considerable cost and effort.

As copper is etched using hydrogen peroxide-based etchant, when excessive copper is dissolved into the etchant, unstable hydrogen peroxide is decomposed to reduce the performance of the etchant.

In addition, the problem of losing its function as a chemical modification of the components such as chelating agents and etch inhibitors in the etchant is often reported.

As a result, when hydrogen peroxide in the etchant is decomposed or other chemical components are chemically denatured, the etching ability of the etchant is inevitably reduced, which causes the replacement cycle of the etchant to be shortened.

Therefore, there is a need for the development of hydrogen peroxide-based etchant with improved stability in use as well as storage in unused conditions.

An object of the present invention is to provide a composition for etching copper, which can suppress the generation of copper precipitates from the composition for etching by increasing the stability of the chelate bond formed between the copper and the organic material.

In addition, an object of the present invention is to provide a copper etching composition which can prevent the dissolved copper from being precipitated as a precipitate as hydrogen peroxide is decomposed when an excessive amount of copper is dissolved into the composition for etching.

In addition, an object of the present invention is to provide a composition for etching copper, which can reduce the decomposition potential of hydrogen peroxide by copper by increasing the dissolving power of the composition for etching.

Another object of the present invention is to provide a hydrogen peroxide-based metal etching composition having excellent stability over time.

Specifically, another object of the present invention is to provide a hydrogen peroxide-based metal etching composition which can prevent the decomposition of hydrogen peroxide in the hydrogen peroxide-based metal etching composition to prevent a sharp drop in the concentration of hydrogen peroxide.

In addition, the present invention improves the stability of the hydrogen peroxide-based metal etching composition by reducing the chemical modification of the other components in the hydrogen peroxide-based metal etching composition, and to provide a composition for hydrogen peroxide-based metal etching that can maintain the etching ability for a long time The purpose.

In order to solve the above technical problem,

According to one aspect of the invention, hydrogen peroxide; At least one chelating agent selected from an acetic acid chelating agent, a sulfonic acid chelating agent and a phosphonic acid chelating agent; Chelate stabilizers represented by the following formula (1); And water; may include a copper etching composition comprising a.

[Formula 1]

Wherein R ₁ to R ₃ are C ₁ -C ₃ alkyl.

In addition, in order to solve the above technical problem,

According to various aspects of the invention, at least one main chelating agent selected from hydrogen peroxide, acetic acid-based chelating agent and amino acid-based chelating agent, sulfuric acid-based first sub chelating agent represented by the following formula 11 or formula 12 or salts thereof, A hydrogen peroxide-based metal etching composition including a phosphate-based second subchelating agent represented by Formula 13 or Formula 14 or a salt thereof, an etching inhibitor, and water may be provided.

[Formula 11]

[Formula 12]

[Formula 13]

[Formula 14]

In Chemical Formula 11 and Chemical Formula 12,

R ₁ to R ₃ are each independently hydrogen, a hydroxyl group, a halogen group, an amino group, a C ₁ -C ₁₀ alkyl group, a C ₁ -C ₁₀ alkoxy group, a C ₁ -C ₁₀ haloalkyl group, a C ₁ -C ₁₀ aminoalkyl group , Phenyl group and halogen-substituted phenyl group,

In Chemical Formula 13 and Chemical Formula 14,

R ₄ to R ₁₂ are each independently hydrogen, a hydroxyl group, a halogen group, an amino group, a C ₁ -C ₁₀ alkyl group, a C ₁ -C ₁₀ alkoxy group, a C ₁ -C ₁₀ haloalkyl group, a C ₁ -C ₁₀ aminoalkyl group , Phenyl group and halogen-substituted phenyl group.

Here, when there exists a functional group containing a nitrogen atom among R <_1> -R <_3> , it is preferable that the said nitrogen atom is a 1, 2 or tetrasubstituted nitrogen atom.

In addition, when a functional group containing a nitrogen atom is present in R ₄ to R ₁₂ , the nitrogen atom is preferably a 1, 2 or tetrasubstituted nitrogen atom.

Additionally, when there is a functional group comprising a carbon atom of R ₄ to R ₁₂ , at least one carbon atom may be substituted with a functional group selected from carboxy group, amino group, amide group, carbamoyl group, nitro group and acetyl group. have.

Copper etching composition according to an embodiment of the present invention can increase the stability of the chelating bond formed between the copper and the organic material by including a chelating stabilizer with a chelating agent to suppress the generation of copper precipitates from the etching composition.

In addition, the copper etching composition according to the present invention can further increase the maximum concentration of soluble copper ions in the etching composition by the additional chelate effect of the chelate stabilizer, thereby preventing decomposition of hydrogen peroxide by excess copper. Can be.

Hydrogen peroxide-based metal etching composition according to another embodiment of the present invention is excellent in stability during long-term storage or use is less likely to decompose hydrogen peroxide in the composition.

In addition, the hydrogen peroxide-based metal etching composition according to the present invention can inhibit the chemical modification of the composition by preventing side reactions between the hydrogen peroxide and other components in the composition, thereby maintaining the etching ability of the hydrogen peroxide-based metal etching composition for a long time have.

Advantages and features of the present invention, and methods for achieving the same will be apparent with reference to the following embodiments. However, the present invention is not limited to the embodiments disclosed below, but may be implemented in various forms. The present embodiments are merely provided to make the disclosure of the present invention complete, and to fully convey the scope of the invention to those skilled in the art, and the present invention is defined by the scope of the claims. It will be. Like reference numerals refer to like elements throughout.

Copper etching composition according to an aspect of the present invention as a hydrogen peroxide-based etchant for wet etching of copper, may include hydrogen peroxide, chelating agent, chelate stabilizer and water.

The hydrogen peroxide (H ₂ O ₂ ) is a hydrogen peroxide-based metal etching composition for the hydrogen peroxide-based metal etching as a proton donor (hydrogen donor) at the same time as a main oxidant to have an etching ability to the metal, such as copper, titanium or molybdenum Contribute to the stability of the composition.

For example, hydrogen peroxide can etch metals such as copper or molybdenum through mechanisms such as Scheme 1 and Scheme 2 below.

Scheme 1

Cu + H ₂ O ₂ ↔ Cu ²⁺ + H ₂ O + 1 / 2O ₂ ↑

Scheme 2

Mo + 3H ₂ O ₂ ↔ Mo ⁶⁺ + 3H ₂ O + 3 / 2O ₂ ↑

As the main oxidizing agent, hydrogen peroxide may be included in an amount of 5 to 40 wt% based on the total weight of the metal etching composition.

When the content of hydrogen peroxide contained in the metal etching composition is less than 5% by weight, there is a concern that the etching ability for metals such as copper or molybdenum may be insufficient, so that the etching may not be performed well or the etching rate may be too slow to be used commercially.

On the other hand, when the content of hydrogen peroxide contained in the metal etching composition exceeds 40% by weight, the etching rate is too fast, difficult to control the etching, there is a fear that over-etching occurs.

The chelating agent may be at least one chelating agent selected from an acetic acid chelating agent, a sulfonic acid chelating agent and a phosphonic acid chelating agent.

More specifically, the acetic acid chelating agent is nitrilotriacetic acid, imino diacetic acid, methylimino diacetic acid, hydroxyethylimino diacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N-hydroxyethylethylenediaminetetraacetic acid At least one selected from methylethylenediaminetetraacetic acid and triethylenetetraaminehexaacetic acid.

In addition, the sulfonic acid chelating agent may be at least one selected from sulfonic acid, methanesulfonic acid, methanedisulfonic acid, ethanesulfonic acid, ethanedisulfonic acid, propanesulfonic acid, benzenesulfonic acid, chlorobenzenesulfonic acid and ethylbenzenesulfonic acid. have.

In addition, the phosphonic acid-based chelating agent may be at least one selected from ethylenediaminetetramethylenephosphonic acid, diethylene triaminepentamethylenephosphonic acid, hydroxyethylidenediphosphonic acid and aminotrimethylene phosphonic acid.

For example, imino diacetic acid, which may be used as a chelating agent of the copper etching composition according to an embodiment of the present invention, has a form in which two carboxyl groups are bonded to nitrogen, which is a central atom, as shown in Formula 2 below.

[Formula 2]

After the acidic protons of the carboxyl groups present at both ends of the iminodiacetic acid are removed, the metal (M; for example, copper) forms chelate bonds with nitrogen, the central atom, and oxygen of the two carboxyl groups, as shown in Formula 3 below. Can be.

[Formula 3]

Referring to Formula 3, the metal (M) forms three bonds with one nitrogen atom and two oxygen atoms in one molecule of iminodiacetic acid, and the metal (M) is represented by By further forming one bond with nodiacetic acid, stable chelate bonds can be maintained.

[Formula 4]

At this time, when the amount of copper dissolved into the copper etching composition is increased, when all of the iminodiacetic acid is consumed as a chelating agent, the amount of copper which forms an unstable chelate bond represented by Formula 3 also increases.

The chelate bond of the structure represented by the formula (3) is unstable chelated state of the metal (M), when left in this state, can be precipitated as a precipitate in the form of copper-iminodiacetic acid.

In addition, since the solubility of chelating agents, such as iminodiacetic acid, is also limited, it is quite difficult to increase the concentration of chelating agents indefinitely to form chelate bonds such as formula (4).

Therefore, according to one embodiment of the present invention, even if the amount of copper dissolved into the copper etching composition is increased, it is possible to form a chelate stabilizer represented by the following Chemical Formula 1 so that it is possible to form a stable chelate bond represented by Chemical Formula 4. It is characterized by including.

[Formula 1]

Here, R ₁ to R ₃ may be C ₁ -C ₃ alkyl, that is, an alkyl chain having 1 to 3 carbon atoms.

The chelate stabilizer represented by Formula 1 is similar to iminodiacetic acid, and after removal of acidic protons of two carboxyl groups bound to a nitrogen atom, which is a central atom, the metal (M; for example, copper) is represented by Formula 5 below. Chelate bonds can be formed.

[Formula 5]

At this time, since when the number of carbon atoms of R ₂ and R ₃ is larger than 3, since the distance between the central atom is nitrogen and the terminal oxygen of both carboxyl groups far to fall is added chelating effect of copper by chelating stabilizing agent, R It is preferable that carbon number of ₂ and R <_3> is three or less.

In addition, the chelating stabilizer provides additional chelating bonds to the copper formed with unstable chelating bonds, as shown in Formula 6, to prevent the occurrence of copper precipitates, as well as to consume the chelating agent to form additional chelate bonds with copper. The amount can be reduced.

[Formula 6]

According to an embodiment of the present invention, the copper etching composition may include 5 to 40 parts by weight of hydrogen peroxide, 1 to 2 parts by weight of chelating agent, 0.1 to 0.4 parts by weight of chelating stabilizer, and a balance of water.

In particular, the weight ratio of the chelating agent to the chelating stabilizer in the copper etching composition is preferably 1: 0.1 to 1: 0.4.

When the ratio of the chelating agent and the chelating stabilizer is 1: 0.1 or less, that is, when the content of the chelating stabilizer is excessively small relative to the content of the chelating agent in the copper etching composition, the chelating agent and the unstable chelate, as shown in the formula (6) Stabilizing effect can be negligible by providing additional chelate bonds to the copper that formed the bonds.

Therefore, when the content of the chelating stabilizer is excessively small relative to the content of the chelating agent in the copper etching composition, there is a high possibility that copper ions forming an unstable chelating bond may precipitate in the form of a copper precipitate.

On the other hand, when the ratio of the chelating agent and the chelating stabilizer is 1: 0.4 or more, that is, the content of the chelating stabilizer to the content of the chelating agent in the copper etching composition is higher than or equal to a predetermined standard, the entire copper etching composition (solvent in which the solute is dissolved) Since the amount of chelating agent and chelating stabilizer that can be dissolved into is limited, there is a possibility that the chelating agent and / or chelating stabilizer is not completely dissolved but is present in the precipitate state.

In particular, in the case of the chelate stabilizer represented by the formula (1), it is very difficult to increase the concentration of the chelate stabilizer indefinitely for the stabilizing effect of the chelate bond because the solubility in the solvent is worse than the chelating agent exemplified in the present invention.

In addition, the maximum concentration of soluble copper ions in the copper etching composition according to an embodiment of the present invention is 6000 ppm or more, it is possible to implement a stable etching characteristics without decomposition of hydrogen peroxide and / or copper precipitates.

In particular, the copper etching composition according to an embodiment of the present invention can solve the problem of precipitation of copper due to unstable chelating bonds by chelating bonds of copper ions by chelating agents and additional chelating bonds by chelating stabilizers, In addition, by additionally supplying a chelating stabilizer, the possibility that two molecules of the chelating agent is consumed for chelating bond of one copper ion with the chelating ion is significantly reduced, even though the same amount of chelating agent is included in one embodiment of the present invention. The copper etching composition according to the present invention has a maximum concentration of soluble copper ions, thereby increasing the life of the copper etching composition, and preventing decomposition of hydrogen peroxide by excessive copper.

Hydrogen peroxide-based metal etching composition according to another aspect of the present invention as a hydrogen peroxide-based etchant for the wet etching of copper, may include hydrogen peroxide, main chelating agent, sub chelating agent, etching inhibitor and water.

Detailed description of the hydrogen peroxide is as described above.

In addition, the metal etching composition according to an embodiment of the present invention further includes a main chelating agent together with hydrogen peroxide.

The main chelating agent assists in etching the metal and at the same time forms a chelating bond with the oxidized form of the metal (ie, metal ions), thereby increasing the stability of the metal ions. 0.1 to 5% by weight may be included.

If the content of the main chelating agent contained in the metal etching composition is less than 0.1% by weight, chelate to metal ions such as copper or molybdenum dissolved in the metal etching composition by the main oxidant is insufficient, resulting in precipitation or excessive dissolution of metal ions. There is a possibility that the etching ability of the metal etching composition is disrupted by the decomposition of hydrogen peroxide by the used metal ions.

On the other hand, when the content of the main chelating agent contained in the metal etching composition exceeds 5% by weight, the etching control is not easy due to the main chelating agent present in excess, or the main chelating agent is precipitated because it exceeds the solubility of the general main chelating agent. Can cause problems.

In one embodiment, acetic acid chelating agents and / or amino acid chelating agents may be used as the main chelating agent.

More specifically, the acetic acid chelating agent may be at least one selected from imino diacetic acid, methylimino diacetic acid, iminomalonic acid and hydroxyethylimino diacetic acid.

In addition, the amino acid chelating agent may be at least one selected from alanine, glutamic acid, aminobutyric acid and glycine.

For example, imino diacetic acid, which can be used as the main chelating agent, has a form in which two carboxyl groups are bonded to nitrogen, which is a central atom, as shown in the following Formula 15.

[Formula 15]

After the acidic protons of the carboxyl groups present at both ends of the iminodiacetic acid are removed, the metal (M; for example, divalent copper ions) chelates with nitrogen as the central atom and oxygen of the two carboxyl groups as shown in the following formula (16). Can be formed.

[Formula 16]

Referring to Formula 16, the metal (M) forms three bonds with one nitrogen atom and two oxygen atoms in one molecule of iminodiacetic acid, and the metal (M) is an iminodi of another molecule as shown in Formula 17 below. By further forming one bond with acetic acid, stable chelate bonds can be maintained.

[Formula 17]

At this time, when the amount of metal ions dissolved into the metal etching composition is increased, when all of the iminodiacetic acid is used as the chelating agent, the amount of copper which forms an unstable chelate bond represented by Formula 16 also increases.

The chelate bond of the structure represented by the formula (16) is a state in which the metal (M) is unstable chelated, and when left in this state for a long time, it may precipitate as a precipitate in the form of metal-iminodiacetic acid.

In addition, since the solubility of the metal etching composition in the main chelating agent such as iminodiacetic acid is also limited, it is quite difficult to increase the concentration of the main chelating agent in the metal etching composition indefinitely to form a chelating bond as shown in Formula 17. .

The above-described problem has been described by way of example using iminodiacetic acid as the main chelating agent, but this problem is not limited to iminodiacetic acid, and it is equally accompanied by other main chelating agents that can form unstable chelating bonds with metals. Can be.

Therefore, according to an embodiment of the present invention, even if the amount of metal ions dissolved into the metal etching composition is increased, it further comprises a subchelating agent in the metal etching composition so that it is possible to form a stable chelate bond represented by the formula (17). Characterized in that.

In addition, the subchelating agent included in the metal etching composition not only assists the chelating bond of the main chelating agent to the metal ions, but also has a certain level of metal etching ability, and maintains pickling of the metal etching composition to maintain the metal etching composition. It can increase the stability and pH retention.

More specifically, the metal etching composition according to an embodiment of the present invention is represented by the sulfuric acid-based first sub chelating agent (or a salt thereof) represented by the following formula (11) or (12) and represented by the following formula (13) or formula (14) It may further comprise a phosphoric acid-based second sub chelating agent (or a salt thereof).

[Formula 11]

[Formula 12]

[Formula 13]

[Formula 14]

In Formula 11 and Formula 12, R ₁ to R ₃ independently of each other, a hydrogen, a hydroxyl group, a halogen group, an amino group, a C ₁ -C ₁₀ alkyl group, a C ₁ -C ₁₀ alkoxy group, a C ₁ -C ₁₀ haloalkyl group , C ₁ -C ₁₀ aminoalkyl group, a phenyl group and a halogen-substituted phenyl group, R ₄ to R ₁₂ in the formula (13) and the formula (14) can be independently of each other hydrogen, hydroxy, halogen, amino, It may be selected from C ₁ -C ₁₀ alkyl group, C ₁ -C ₁₀ alkoxy group, C ₁ -C ₁₀ haloalkyl group, C ₁ -C ₁₀ aminoalkyl group, phenyl group and halogen-substituted phenyl group.

In another embodiment, when the functional group containing a carbon atom of R ₄ to R ₁₂ is present, at least one carbon atom is selected from a carboxy group, an amino group, an amide group, a carbamoyl group, a nitro group, and an acetyl group. Can be substituted with a functional group.

The sulfuric acid first subchelating agent (or a salt thereof) represented by Formula 11 or Formula 12 and the phosphoric acid second subchelating agent (or a salt thereof) represented by Formula 13 or Formula 14 below are represented by an oxygen or nitrogen atom. By providing additional chelate bonds to the metal ions that form partial chelate bonds with the main chelating agent, the metal ions can be stably chelated.

At this time, when there is a functional group containing a nitrogen atom among R ₁ to R ₁₂ , the nitrogen atom is preferably a 1, 2 or tetrasubstituted nitrogen atom.

The metal etching composition according to an embodiment of the present invention includes hydrogen peroxide having a strong oxidizing power, and hydrogen peroxide may cause an oxidation reaction with other compounds in the metal etching composition.

In particular, compounds containing tertiary amines or tertiary amino groups mainly used as chelating agents (main chelating agents and subchelating agents) can react with hydrogen peroxide to form N-oxides as shown in Scheme 3 below.

Scheme 3

_{R 3 N: + H 2 O} 2 → R 3 N + -O - + H 2 O

When the compound containing the tertiary amine or the tertiary amino group is oxidized to form N-oxide, the properties of the existing tertiary amine or the compound containing the tertiary amino group, especially pKa, etc., change.

For example, in the case of aminotris (methylenephosphonic acid) as a chelating agent of the metal etching composition, since it has three phosphonic acid substituents, it has a pKa value of six steps in the range of 0.3-12.2.

Therefore, as the etching proceeds, even though the metal ions are dissolved into the etching composition, the aminotris (methylenephosphonic acid) can supply protons in stages so that the pH of the etching composition can be stably maintained.

As described above, aminotris (methylenephosphonic acid) has a plurality of phosphonic acid substituents that can assist chelation of metal ions, and at the same time, a composition for etching metals by stepwise proton supply characteristics by a plurality of phosphonic acid substituents It is mainly used as a chelating agent.

However, aminotris (methylenephosphonic acid) is a tertiary amine compound, and may react with hydrogen peroxide to form N-oxide as shown in Scheme 4 below.

Scheme 4

The N ⁺ -O ^- bond of the N-oxide produced by the above Scheme 4 is a coordination bond and a bond by donation of the outermost electron of the nitrogen atom.

In addition, due to the difference in electronegativity between the nitrogen atom 3.0 and the oxygen atom 3.5, the nitrogen atom and the oxygen atom are substantially in a state where the charge is separated.

N ⁺ -O ^- coordination bond has a polarity by the charge separation of the nitrogen and oxygen atoms as described above, the polarity of the N ⁺ -O ^- coordination bond is characterized in the characteristics of the phosphonic acid substituent bonded to the nitrogen atom, in particular pKa Will be affected.

Although the pKa of the pH and / or chelating agent (main chelating agent and / or subchelating agent) of the metal etching composition during metal etching must be designed with great precision to minimize changes in the quality characteristics of the etching result, the reaction scheme Side reactions of hydrogen peroxide with chelating agents, such as 4, act as a cause of changing the pH of the metal etch composition as well as the pKa of the chelating agent (main chelating agent and / or sub chelating agent).

Therefore, when there is a functional group containing a nitrogen atom in R ₁ to R ₁₂ , the nitrogen atom is preferably not a trisubstituted nitrogen atom.

In addition, the first subchelating agent and the second subchelating agent included in the metal etching composition according to an embodiment of the present invention is preferably a compound other than a compound containing a tertiary amine or a tertiary amino group, and the main chelate The agent is also preferably a compound other than a compound containing a tertiary amine or tertiary amino group.

As the main chelating agent satisfying the above conditions, at least one compound selected from iminodiacetic acid, methyliminodiacetic acid, iminomalonic acid, hydroxyethyliminodiacetic acid, alanine, glutamic acid, aminobutyric acid and glycine may be used. .

Further, as the first subchelating agent, sulfonic acid, methanesulfonic acid, methanedisulfonic acid, ethanesulfonic acid, ethanedisulfonic acid, propanesulfonic acid, benzenesulfonic acid, chlorobenzenesulfonic acid, ethylbenzenesulfonic acid, potassium bisulfate, potassium At least one compound selected from sulfate, sodium bisulfate, sodium sulfate, ammonium sulfate, ammonium persulfate, dimethyl sulfoxide and diethyl sulfoxide may be used, and the second subchelating agent may be aminoethylphosphonic acid, carboxyethyl At least one selected from phosphonic acid, dimethylphosphate, dimethylphosphonate, hydroxyethylidenediphosphonic acid, methylenediphosphonic acid, hydroxyphosphonocarboxylic acid, methylenediphosphonocarboxylic acid and phosphonobutane-tris-carboxylic acid Compounds can be used.

On the other hand, chelating agents (main chelating agents and sub chelating agents) which are not suitable for the metal etching composition according to an embodiment of the present invention include aminotris (methylenephosphonic acid), N, N-bis (phosphonomethyl) glycine, Diethylenetriaminepenta (methylenephosphonic acid), ethylenediaminetetra (methylenephosphonic acid), hexamethylenediaminetetra (methylenephosphonic acid), N- (phosphonomethyl) iminodiacetic acid, tetramethylenediaminetetra (methylene Phosphonic acid).

According to one embodiment of the present invention, the first subchelating agent and the second subchelating agent in the metal etching composition is preferably used in combination.

In this case, the content of the first sub chelating agent in the metal etching composition is preferably 0.5 to 2.0% by weight, the content of the second sub chelating agent is preferably 0.1 to 1.6% by weight.

In particular, the weight ratio of the first subchelating agent and the second subchelating agent in the metal etching composition is preferably in the range of 6: 4 to 9: 1.

The first subchelating agent which can be used according to an embodiment of the present invention is a sulfuric acid-based chelating agent has excellent stability over time, while the second subchelating agent is a phosphate-based chelating agent of the metal etching ability and the composition for etching metal Pickling retention is excellent.

When the weight ratio of the first subchelating agent and the second subchelating agent in the metal etching composition is less than 6: 4 (for example, 0.5: 9.5), the stability of the metal etching composition with time decreases, thereby changing the time and the amount of metal. As a result, the EPD may be slowed, or the etchable component of the metal etching composition may be more likely to be decomposed.

On the other hand, when the weight ratio of the first sub chelating agent and the second sub chelating agent in the metal etching composition exceeds 9: 1 (for example, 9.5: 0.5), the EPD may be slowed due to insufficient etching ability of the metal, Poor pickling retention may reduce the pH stability of the metal etching composition.

In addition, when the content of the first subchelating agent and the second subchelating agent in the metal etching composition is less than 0.5% by weight and 0.1% by weight, respectively, the main chelating agent may not be able to sufficiently perform the chelating assistant role, and as a proton donor. May have insufficient ability to act to stabilize the pH of the metal etching composition.

On the other hand, when the content of the first sub chelating agent and the second sub chelating agent contained in the metal etching composition exceeds 2% by weight and 1.6% by weight, respectively, it is not easy to control the etching by the excessively present subchelating agent Otherwise, there may occur a problem that precipitates exceeding the solubility of the sub chelating agent in the metal etching composition.

In addition, the composition for etching metal according to an embodiment of the present invention may further include an etching inhibitor to obtain an etching result of excellent quality by adjusting the etching rate of the metal.

The etching inhibitor may be included in an amount of 0.5 to 1.5 wt% based on the total weight of the metal etching composition.

If the content of the etching inhibitor contained in the metal etching composition is less than 0.5% by weight, there is a possibility that the etching rate of the metal may be excessively high and the quality of the etching result may decrease, whereas the content of the etching inhibitor contained in the metal etching composition is 1.5. If the weight percentage is exceeded, there is a possibility that the etching rate is lowered and the productivity is lowered.

In addition, for the same reason as the chelating agent, the etching inhibitor included in the metal etching composition according to an embodiment of the present invention is preferably a compound other than a compound containing a tertiary amine or a tertiary amino group.

Accordingly, etching inhibitors include furan, thiophene, pyrrole, oxazole, imidazole, pyrazole, triazole, tetrazole, aminotetrazole, methyltetrazole, piperazine, methylpiperazine, hydroxyethylpiperazine, At least one compound selected from pyrrolidine, aloxane, benzofuran, benzothiophene, indole, benzimidazole, benzpyrazole, tolutriazole, hydrotolutriazole and hydroxytolutriazole is used. The pyridine-based compound capable of reacting with hydrogen peroxide to form N-oxide is not suitable as an etching inhibitor used in the metal etching composition according to the embodiment of the present invention.

In addition to the above-described components, the metal etching composition according to an embodiment of the present invention may further include additional components such as a corrosion inhibitor, a surfactant, a pH adjusting agent, an undercut inhibitor or a residue inhibitor.

The following presents specific embodiments of the present invention. However, the embodiments described below are merely for illustrating or explaining the present invention in detail, and thus the present invention is not limited thereto.

Composition of Copper Etching Composition

Table 1 below shows the compositions of the copper etching compositions according to Examples and Comparative Examples.

division	Hydrogen peroxide	Chelating agents	Other ingredients
Example 1	23 wt%	Imino diacetic acid 2wt%	Formula 70.2wt%
Example 2	23 wt%	Imino diacetic acid1wt%	Formula 80.4wt%
Example 3	23 wt%	N-methyliminodiacetic acid 1wt%	Formula 70.2wt%
Example 4	23 wt%	N-methyliminodiacetic acid 2wt%	Formula 80.4wt%
Example 5	23 wt%	Methanesulfonic acid	Formula 70.2wt%
Example 6	23 wt%	Benzene sulfonic acid 1wt%	Formula 70.2wt%
Example 7	23 wt%	Hydroxyethylidenediphosphonic acid 1wt%	Formula 70.2wt%
Example 8	23 wt%	Ethylenediaminetetramethylenephosphonic acid1wt%	Formula 70.2wt%
Comparative Example 1	23 wt%	Imino diacetic acid1wt%	-
Comparative Example 2	23 wt%	Imino diacetic acid 2wt%	-
Comparative Example 3	23 wt%	Imino diacetic acid 2wt%	N-methyliminodiacetic acid 0.2wt%
Comparative Example 4	23 wt%	Imino diacetic acid 2wt%	0.3 wt% of N, N-bis (carboxymethyl) ethanolamine
Comparative Example 5	23 wt%	Imino diacetic acid 2wt%	Triethylenetetraaminehexaacetic acid0.25wt%
Comparative Example 6	23 wt%	Imino diacetic acid 2wt%	70.05 wt%
Comparative Example 7	23 wt%	Methanesulfonic acid	-
Comparative Example 8	23 wt%	Methanesulfonic acid	N-methyliminodiacetic acid0.2wt%
Comparative Example 9	23 wt%	Hydroxyethylidenediphosphonic acid 1wt%	-
Comparative Example 10	23 wt%	Hydroxyethylidenediphosphonic acid 1wt%	N-methyliminodiacetic acid0.2wt%

* Include remaining water

[Formula 7]

[Formula 8]

Evaluation of Properties of Copper Etching Compositions

In order to evaluate the characteristics of the copper etching composition having the composition of Table 1, the copper etching composition according to the Examples and Comparative Examples were put into the spray equipment of wet etching method (manufactured by KCTECH, model name: ETCHER (TFT)) Etching was performed on a copper substrate with a thickness of 2000 kPa when the temperature was maintained at 33 ± 0.5 ° C. by heating.

The characteristic evaluation item for evaluating the stability of the copper etching composition is whether or not the etchant generated precipitates at a copper ion concentration of 6000 ppm and the concentration of copper ions that can be dissolved in maximum.

The results for the two evaluation items are shown in Table 2 below.

division	Precipitation	Maximum dissolved copper ion concentration (ppm)
Example 1	radish	8000
Example 2	radish	7500
Example 3	radish	7000
Example 4	radish	8000
Example 5	radish	6000
Example 6	radish	6000
Example 7	radish	6000
Example 8	radish	6000
Comparative Example 1	U	5000
Comparative Example 2	U	6000
Comparative Example 3	U	7500
Comparative Example 4	U	8000
Comparative Example 5	U	9000
Comparative Example 6	U	7000
Comparative Example 7	U	4000
Comparative Example 8	U	5500
Comparative Example 9	U	5000
Comparative Example 10	U	6500

Examples 1 to 4 are copper etching compositions comprising an acetic acid-based chelating agent, Examples 5 and 6 are copper etching compositions comprising a sulfonic acid-based chelating agent, Examples 7 and 8 are phosphone As a composition for copper etching including an acid chelating agent, Examples 1 to 8 included the chelating stabilizer represented by the formula (7) or formula (8) in an amount of 0.1 to 0.4% by weight relative to the weight of the total copper etching composition.

On the other hand, Comparative Example 1 and Comparative Example 2 is a copper etching composition containing only a chelating agent without a chelating stabilizer, although the maximum soluble copper ion concentration increases as the content of the chelating agent increases, copper-iminodiacetic acid It was confirmed that a precipitate of the form occurred.

In addition, Comparative Examples 3 to 5 includes an iminodiacetic acid as an acetic acid-based chelating agent, and further includes a component (for example, an auxiliary chelating agent) that is usually used as an additive of a copper etching composition. When the composition further comprises N-methyliminodiacetic acid, N, N-bis (carboxymethyl) ethanolamine and triethylenetetraaminehexaacetic acid as auxiliary chelating agents, the maximum soluble copper ion concentration of the copper etching composition is It was confirmed that the commercialization level was reached at 7500 to 9000 ppm.

However, as the etching proceeds according to Comparative Examples 3 to 5, it was confirmed that the copper precipitates were generated. At this time, the generation of copper precipitates was a phenomenon observed even though the maximum dissolved copper ion concentration of the copper etching composition was not reached.

This phenomenon is a compound having a different structure from the chelate stabilizer represented by the formula 1, N-methylimino diacetic acid, N, N-bis (carboxymethyl) ethanolamine and triethylene tetraamine hexaacetic acid, The stabilizer was not able to provide an effect of compensating for the unstable chelating bond between the copper ions and the chelating agent, and it was confirmed that the copper-chelating agent forming the unstable chelating bond was precipitated in the form of a precipitate.

In addition, the composition for etching copper according to Comparative Example 6 includes an imino diacetic acid as the acetic acid-based chelating agent, as in the embodiment of the present invention contained a chelating stabilizer represented by the formula (7). However, the content of the chelate stabilizer is 0.05% by weight relative to the weight of the total copper etching composition, which is lower than the content of the chelate stabilizer included in the examples.

Similarly, in the case of Comparative Example 6, as the etching proceeds, copper precipitates were generated, which is too low in the amount of the chelating stabilizer relative to the content of the chelating agent in the copper etching composition, such as the structure represented by the formula (6), chelate It was confirmed that the effect of stabilizing was negligible by providing additional chelate bonds to the copper which formed unstable chelate bonds with the agent.

Further, in addition to Comparative Examples 7 and 9, each containing a sulfonic acid chelating agent or a phosphonic acid chelating agent alone, Comparative Example 8 and a phosphonic acid chelating agent and an auxiliary chelating agent are used in combination. In the case of Comparative Example 10 in which a mixture is used, as the etching proceeds, it was confirmed that the copper precipitates were generated even though the maximum dissolvable concentration of the copper ions of the composition for copper etching was not reached.

Composition of hydrogen peroxide based metal etching composition

Table 3 below shows the composition of the hydrogen peroxide-based metal etching compositions according to Examples and Comparative Examples.

Configuration	Hydrogen peroxide	Main Chelating Agent (A)		First Subchelating Agent (B)		Second Subchelating Agent (C)		B: C content ratio	Etch inhibitor (D)
Example 9	23	A-1	2.5	B-1	1.2	C-1	0.8	6: 4	D-1	1.0
Example 10	23	A-1	2.5	B-2	1.2	C-2	0.8	6: 4	D-1	1.0
Example 11	23	A-2	2.5	B-1	1.4	C-1	0.6	7: 3	D-1	1.0
Example 12	23	A-2	2.5	B-2	1.4	C-2	0.6	7: 3	D-1	1.0
Example 13	23	A-2	2.5	B-2	1.8	C-2	0.2	9: 1	D-1	1.0
Comparative Example 11	23	A-1	2.5	B-1	2.0	-	-	-	D-1	1.0
Comparative Example 12	23	A-1	2.5	B-2	2.0	-	-	-	D-1	1.0
Comparative Example 13	23	A-1	2.5	-	-	C-1	2.0	-	D-1	1.0
Comparative Example 14	23	A-1	2.5	-	-	C-2	2.0	-	D-1	1.0
Comparative Example 15	23	A-1	2.5	-	-	C-3	2.0	-	D-1	1.0
Comparative Example 16	23	A-3	2.5	B-1	1.2	C-1	0.8	6: 4	D-1	1.0
Comparative Example 17	23	A-1	2.5	B-1	1.2	C-3	0.8	6: 4	D-1	1.0
Comparative Example 18	23	A-1	2.5	B-1	1.2	C-1	0.8	6: 4	D-2	1.0

* Unit: weight%

* A-1: imino diacetic acid; A-2: glycine; A-3: nitrilotriacetic acid; B-1: methanesulfonic acid; B-2: ammonium persulfate; C-1: hydroxyethylidene diphosphonic acid; C-2: methylenediphosphonic acid; C-3: aminotris (methylenephosphonic acid); D-1: pyrrole; D-2: pyridine.

In Comparative Examples 11 and 12, only the first subchelating agent, which is a sulfuric acid subchelating agent, is included as the subchelating agent, and in Comparative Examples 13 to 15, a phosphoric acid subchelating agent is used as the subchelating agent. It is the case containing only 2 subchelating agents.

In particular, in the case of Comparative Example 15, a second subchelating agent containing a tertiary amino group was used.

In Comparative Example 16, the same kind of first and second subchelating agents as in Example were used, but nitrilotriacetic acid was used as the main chelating agent.

In Comparative Example 17, the first subchelating agent and the second subchelating agent were mixed at a weight ratio of 6: 4, but at this time, the second subchelating agent used a compound containing a tertiary amino group.

In Comparative Example 18, a first subchelating agent and a second subchelating agent of the same kind as in Example were used, but pyridine was used as an etching inhibitor.

Characterization of Hydrogen Peroxide Metal Etching Compositions

Table 4 shows the extent to which the characteristics of the metal etching composition changes over time according to the components of the hydrogen peroxide-based metal etching composition having the composition shown in Table 3.

The experimental temperature was room temperature and evaluated at 25 ° C. and 30 ° C. in consideration of seasonal characteristics. In addition, since the metal etching composition is usually used within 30 days from the production date, the change in properties up to 30 days was observed.

All measurements are expressed as a percentage of change on day 0, i.e., measured immediately upon preparation.

The degree of perhydrolysis was a change relative to the initial concentration of hydrogen peroxide, measured by potassium permanganate (KmnO ₄ ) titration, and calculated according to Equation 1 below.

[Equation 1]

(Content of hydrogen peroxide (wt%) / initial hydrogen peroxide (wt%) on day 15 or 30)) x 100

Component denaturation is a change relative to the concentration of the initial additives (first sub chelating agent and second sub chelating agent), the content of the first sub chelating agent and the second sub chelating agent by IC-ion analysis method, respectively, Calculated according to Eq.

[Equation 2]

(Content of wt% of first and second subchelating agents (wt%) / initial first and second subchelating agents (wt%) of day 15 or 30) x 100

EPD (End Point Detection) means the time taken until the end of the etching, EPD change is a change compared to the initial EPD, the EPD was measured by visually observing the substrate and confirmed through SEM analysis. Calculated according to equation 3.

 [Equation 3]

(EPD measurement value in seconds / initial EPD measurement value in seconds on the 15th or 30th day) × 100

Configuration	Temperature (℃)	Perhydrolysis degree (%)		Component Denaturity (%)		EPD% change
		15d	30d	15d	30d	15d	30d
Example 9	25	-1.0	-2.5	0	-0.5	-1.0	+1.0
	30	-2.6	-8.7	-0.4	-0.8	+0.8	+7.0
Example 10	25	-1.0	-3.0	0	-0.5	0	+1.0
	30	-2.7	-9.0	-0.5	-0.7	+1.0	+7.5
Example 11	25	-1.1	-3.2	0	-0.5	+0.5	+1.0
	30	-2.7	-9.1	-0.5	-0.85	+1.0	+8.1
Example 12	25	-1.2	-3.5	0	-0.45	+0.5	+1.0
	30	-3.3	-9.2	-0.5	-0.8	+1.2	+7.9
Example 13	25	-1.0	-3.5	0	-0.5	+0.5	+1.5
	30	-2.9	-9.5	-0.5	-0.9	+1.5	+9.3
Comparative Example 11	25	-1.5	-5.1	0	-0.65	+1.0	+3.8
	30	-4.5	-16.0	-0.5	-1.2	+4.0	+13.6
Comparative Example 12	25	-2.0	-6.5	0	-0.6	+1.0	+3.5
	30	-5.5	-17.3	-0.55	-1.1	+4.0	+12.6
Comparative Example 13	25	-1.6	-5.6	0	-1.8	+0.7	+4.0
	30	-6.6	-15.2	-1.8	-1.8	+4.5	+14.3
Comparative Example 14	25	-1.8	-5.2	0	-1.9	+0.8	+4.8
	30	-6.2	-16.6	-2.6	-2.6	+5.2	+15.3
Comparative Example 15	25	-2.7	-9.8	-14.3	-30.6	+10.5	+30.1
	30	-11.2	-24.7	-26.6	-65.7	+28.3	+50.7
Comparative Example 16	25	-1.9	-8.3	0	-0.35	+3.7	+18.1
	30	-11.0	-23.0	-0.5	-0.7	+22.3	+40.5
Comparative Example 17	25	-1.5	-8.1	-15.0	-32.7	+8.8	+23.2
	30	-10.7	-20.3	-30.8	-63.5	+29.9	+48.0
Comparative Example 18	25	-1.3	-4.9	0	-0.3	0	-0.5
	30	-4.5	-10.1	-0.4	-0.8	+0.5	+5.0

* 15D: measured value at 15 days; 30D: measured value on day 30.

Table 5 shows the extent to which the characteristics of the metal etching composition changes over time during etching using the hydrogen peroxide-based metal etching composition having the composition shown in Table 3.

The experimental temperature is 33 ° C., which is a typical etching temperature, and all evaluation values are 0 ppm, i.e., 2,500 ppm of copper powder is added into the metal etching composition based on the value measured without adding copper powder into the metal etching composition. The degree of change when the copper powder of 5,000 ppm and when added.

Configuration	Temperature (℃)	Perhydrolysis degree (%)		Component Denaturity (%)		EPD% change
		2500 ppm	5000 ppm	2500 ppm	5000 ppm	2500 ppm	5000 ppm
Example 9	33	-0.5	-2.5	0	-0.05	-0.5	+1.0
Example 10	33	-0.5	-2.6	0	-0.05	+0.5	+2.0
Example 11	33	-0.5	-2.8	0	-0.1	+0.8	+2.5
Example 12	33	-0.8	-3.0	0	-0.05	+0.8	+2.3
Example 13	33	-0.9	-3.0	0	-0.1	+1.0	+3.0
Comparative Example 11	33	-2.0	-5.2	-0.05	-0.25	+3.0	+7.8
Comparative Example 12	33	-2.0	-5.3	-0.05	-0.2	+2.8	+7.0
Comparative Example 13	33	-1.7	-5.0	-0.1	-0.3	+3.0	+8.2
Comparative Example 14	33	-1.8	-5.2	-0.1	-0.3	+3.5	+8.5
Comparative Example 15	33	-2.1	-8.6	-0.1	-0.5	+5.3	+14.0
Comparative Example 16	33	-1.7	-8.5	0	-0.05	+3.7	+11.2
Comparative Example 17	33	-1.5	-7.3	-0.1	-0.45	+4.5	+13.8
Comparative Example 18	33	-1.6	-5.1	0	-0.05	-0.5	+0.5

Referring to the evaluation values described in Table 4 and Table 5, it can be seen that the characteristics over time according to the type and content of the main chelating agent, the first sub chelating agent and the second sub chelating agent contained in the metal etching composition.

As in Comparative Examples 11 and 12, only the first subchelating agent, which is a sulfuric acid subchelating agent, as the subchelating agent, or as the subchelating agent, the second subchelating agent, which is a phosphoric acid subchelating agent, as the Comparative Examples 13 to 15 In the case of containing only the agent, it was confirmed that the degree of perhydrolysis, component denaturation, and EPD were all larger than those of the examples.

Particularly, in Comparative Example 15, the degree of perhydrolysis, component denaturation and EPD change was significantly higher than that of Comparative Examples 11 to 14, which is aminotris (methylene) which is the second subchelating agent used in Comparative Example 15. Phosphonic acid) is expected to result from reaction with hydrogen peroxide to form N-oxide.

In addition, in Comparative Examples 16 to 18, nitrilotriacetic acid, aminotris (methylenephosphonic acid) and pyridine are used as materials capable of reacting with hydrogen peroxide to form N-oxide, respectively. As in 15, hydrogen peroxide and the compound react with each other to form N-oxide, it was confirmed that the degree of perhydrolysis, component denaturation and EPD change increased.

As mentioned above, although an embodiment of the present invention has been described, those of ordinary skill in the art may add, change, delete or add components within the scope not departing from the spirit of the present invention described in the claims. The present invention may be modified and changed in various ways, etc., which will also be included within the scope of the present invention.

Claims (17)

1. Hydrogen peroxide;

   At least one chelating agent selected from an acetic acid chelating agent, a sulfonic acid chelating agent and a phosphonic acid chelating agent;

   Chelate stabilizers represented by the following formula (1); And

   water;

   As a composition for copper etching comprising:

   The weight ratio of the chelating agent and the chelate stabilizer in the copper etching composition is 1: 0.1 to 1: 0.4,

   Copper Etch Composition:

   [Formula 1]

   

   Wherein R ₁ to R ₃ are C ₁ -C ₃ alkylene.
2. The method of claim 1,

   5 to 40 parts by weight of the hydrogen peroxide;

   1 to 2 parts by weight of the chelating agent;

   0.1 to 0.4 parts by weight of the chelate stabilizer; And

   Residual amount of water;

   Including,

   Copper etching composition.
3. The method of claim 1,

   The acetic acid chelating agent is nitrilotriacetic acid, imino diacetic acid, methylimino diacetic acid, hydroxyethylimino diacetic acid, diethylenetriamine pentaacetic acid, ethylenediaminetetraacetic acid, N-hydroxyethylethylenediaminetetraacetic acid, methylethylene At least one selected from diaminetetraacetic acid and triethylenetetraamine hexaacetic acid,

   Copper etching composition.
4. The method of claim 1,

   The sulfonic acid chelating agent is at least one selected from sulfonic acid, methanesulfonic acid, methane disulfonic acid, ethanesulfonic acid, ethanedisulfonic acid, propanesulfonic acid, benzenesulfonic acid, chlorobenzenesulfonic acid and ethylbenzenesulfonic acid,

   Copper etching composition.
5. The method of claim 1,

   The phosphonic acid chelating agent is at least one selected from ethylenediamine tetramethylene phosphonic acid, diethylene triamine pentamethylene phosphonic acid, hydroxyethylidenediphosphonic acid and aminotrimethylene phosphonic acid,

   Copper etching composition.
6. The method of claim 1,

   The maximum concentration of soluble copper ions in the copper etching composition is 6000 ppm or more,

   Copper etching composition.
7. Hydrogen peroxide;

   At least one main chelating agent selected from acetic acid chelating agents and amino acid chelating agents;

   Sulfuric acid-based first chelating agents represented by the following general formula (11) or general formula (12) or salts thereof;

   A phosphoric acid second subchelating agent represented by the following Formula 13 or Formula 14 or a salt thereof;

   Etching inhibitors; And

   water;

   Including,

   Hydrogen peroxide based metal etching composition:

   [Formula 11]

   

   [Formula 12]

   

   [Formula 13]

   

   [Formula 14]

   

   In Chemical Formula 11 and Chemical Formula 12,

   R ₁ to R ₃ are each independently hydrogen, a hydroxyl group, a halogen group, an amino group, a C ₁ -C ₁₀ alkyl group, a C ₁ -C ₁₀ alkoxy group, a C ₁ -C ₁₀ haloalkyl group, a C ₁ -C ₁₀ aminoalkyl group , Phenyl group and halogen-substituted phenyl group,

   In Chemical Formula 13 and Chemical Formula 14,

   R ₄ to R ₁₂ are each independently hydrogen, a hydroxyl group, a halogen group, an amino group, a C ₁ -C ₁₀ alkyl group, a C ₁ -C ₁₀ alkoxy group, a C ₁ -C ₁₀ haloalkyl group, a C ₁ -C ₁₀ aminoalkyl group , Phenyl group and halogen-substituted phenyl group.
8. The method of claim 7, wherein

   In the hydrogen peroxide-based metal etching composition, the weight ratio of the first subchelating agent and the second subchelate is in the range of 6: 4 to 9: 1,

   Hydrogen peroxide-based metal etching composition.
9. The method of claim 7, wherein

   When there is a functional group containing a nitrogen atom of R ₁ to R ₃ , the nitrogen atom is a 1, 2 or tetrasubstituted nitrogen atom,

   Hydrogen peroxide-based metal etching composition.
10. The method of claim 7, wherein

    The first subchelating agent is sulfonic acid, methanesulfonic acid, methanedisulfonic acid, ethanesulfonic acid, ethanedisulfonic acid, propanesulfonic acid, benzenesulfonic acid, chlorobenzenesulfonic acid, ethylbenzenesulfonic acid, potassium bisulfate, potassium sulfate At least one selected from sodium bisulfate, sodium sulfate, ammonium sulfate, ammonium persulfate, dimethyl sulfoxide and diethyl sulfoxide,

    Hydrogen peroxide-based metal etching composition.
11. The method of claim 7, wherein

    When there is a functional group containing a nitrogen atom of R ₄ to R ₁₂ , the nitrogen atom is 1, 2 or tetrasubstituted nitrogen atom,

    Hydrogen peroxide-based metal etching composition.
12. The method of claim 11,

    Wherein the second subchelating agent is at least one selected from aminoethylphosphonic acid, carboxyethylphosphonic acid, dimethylphosphate, dimethylphosphonate, hydroxyethylidenediphosphonic acid and methylenediphosphonic acid

    Hydrogen peroxide-based metal etching composition.
13. The method of claim 7, wherein

    When there is a functional group including a carbon atom of R ₄ to R ₁₂ , at least one carbon atom is substituted with a functional group selected from a carboxy group, an amino group, an amide group, a carbamoyl group, a nitro group, and an acetyl group,

    Hydrogen peroxide-based metal etching composition.
14. The method of claim 13,

    Wherein said second subchelating agent is at least one selected from hydroxyphosphonocarboxylic acid, methylenediphosphonocarboxylic acid and phosphonobutane-tris-carboxylic acid

    Hydrogen peroxide-based metal etching composition.
15. The method of claim 7, wherein

    The acetic acid chelating agent is at least one selected from imino diacetic acid, methylimino diacetic acid, iminomalonic acid and hydroxyethylimino diacetic acid,

    Hydrogen peroxide-based metal etching composition.
16. The method of claim 7, wherein

    The amino acid chelating agent is at least one selected from alanine, glutamic acid, aminobutyric acid and glycine,

    Hydrogen peroxide-based metal etching composition.
17. The method of claim 7, wherein

    The etch inhibitor is furan, thiophene, pyrrole, oxazole, imidazole, pyrazole, triazole, tetrazole, aminotetrazole, methyltetrazole, piperazine, methylpiperazine, hydroxyethylpiperazine, pyrrolidine At least one selected from aloxane, benzofuran, benzothiophene, indole, benzimidazole, benzpyrazole, tolutriazole, hydrotolutriazole and hydroxytolutriazole,

    Hydrogen peroxide-based metal etching composition.