KR101916157B1 - Etchant additives and etchant using the same - Google Patents

Abstract

The present invention relates to an etching additive for controlling the etching rate for controlling the etching direction, an etching solution containing the etching additive, and a method of manufacturing a wiring using the etching additive.
In the case of using the etching additive of the present invention, the etching rate and direction in the vertical and horizontal directions can be controlled in the etching process for forming a circuit, so that the top portion from the bottom portion of the circuit has a 1: 1 ratio It is possible to secure a linearity close to that of the circuit and to achieve a high etch factor close to the infinite etch factor of the circuit.

Description

TECHNICAL FIELD [0001] The present invention relates to an etchant additive and an etchant using the etchant. [0002] ETCHANT ADDITIVES AND ETCHANT USING THE SAME [0003]

The present invention relates to an etching additive for controlling the etching rate for controlling the etching direction, an etching solution containing the etching additive, and a method of manufacturing a wiring using the etching additive.

Electronic devices such as smart phones, tablet PCs, notebooks, and the like have been rapidly developed, and electronic devices are being developed as miniaturization, lightweight, and thinning technology. Therefore, an electronic circuit board having high reliability, capable of mounting a high-density, highly integrated component is required, and in the printed wiring board industry, it is strongly demanded to provide a high-density wiring board at low cost. Currently, there is a method of manufacturing a printed-wiring board used for micro-circuit processing, including a subtractive method in which a circuit is formed by etching the remaining portion except a portion where a circuit is formed on a copper-clad laminate, and a plating method There is an additive method that directly forms the necessary circuitry. In the case of the additive method, a high cost is incurred, so a technique capable of supplementing and replacing the additive method is required.

However, in the conventional subtractive method, since the circuit pattern formation by etching is isotropic, it is difficult to make the etching to have directionality, so that there is a problem that it is difficult to realize high-density wiring at low cost. When a circuit is formed by using an etching solution such as general iron chloride etching type, chlorinated copper etching type, alkali etching type, hydrogen peroxide and sulfuric acid etching type, it is difficult to control the etching speed and direction, (top) has additional linearity, or it is difficult to realize a high etching factor.

The object of the present invention is to provide an etchant additive for controlling the etching rate and direction in the etching process for forming a circuit and to ensure that the top portion from the bottom portion of the circuit is maximally close to 1: And an etchant additive that realizes a high etching factor so that an etch factor of the circuit is formed close to infinity, an etchant containing the etchant, and a method of manufacturing a wiring using the etchant.

The present invention also provides a method of forming a circuit using a metal or a metal alloy and a method of etching the same using an etching solution such as a general iron chloride etching type, a chlorinated copper etching type, an alkaline etching type, a hydrogen peroxide and a sulfuric acid etching type An etching solution containing the etching additive, and a method of manufacturing a wiring using the etching solution.

According to an aspect of the present invention, there is provided an etching solution used in an etching process of an electrical circuit wiring made of a metal. The etching solution contains an organometallic modified coating on a metal surface and an etching additive containing a component exhibiting an etching- . More specifically, an etching additive that makes it possible to keep the etching rate in the horizontal direction and concentrate the etching in the vertical direction so that the top portion of the circuit can be secured close to the ratio of 1: 1 .

The etching additive of the present invention is characterized by enabling anisotropic etching, i.e., a high etching factor.

It is difficult to realize a 1: 1 ratio between the top and bottom portions of the circuit because the etching speeds in the vertical direction and the horizontal direction are almost similar in the etching process for general circuit formation, so that a high etching factor can be realized I can not. The inventors of the present invention have found that it is necessary to use an appropriate etching inhibitor to suppress the etching in the horizontal direction and concentrate the etching force in the vertical direction in order to realize a high etching factor. As a result of the study on the etching inhibitor, any one selected from azole compounds, triazole compounds, tetrazole compounds, imidazole compounds and thiazole compounds, or mixtures thereof, polymer amine compounds and amine compounds are mixed in a specific amount range The present invention has been completed.

The present invention relates to (A) at least one compound selected from inorganic acids, basic hydroxides and alcohols,

(B) at least one compound selected from triazole-based compounds, tetrazole-based compounds, imidazole-based compounds and thiazole-based compounds,

(C) a polymeric amine compound and

(D) an amine-based compound.

The present invention also relates to an etching solution for wiring production comprising the etching additive.

In the case of using the etching additive of the present invention, the etching rate and direction in the vertical and horizontal directions can be controlled in the etching process for forming a circuit, so that the top portion from the bottom portion of the circuit has a 1: 1 ratio It is possible to obtain a high etch factor close to infinite in the etch factor of the circuit.

According to the present invention, at least one metal selected from copper, copper alloy, nickel, chromium, nickel chromium alloy, and palladium can be rapidly etched, and excessive dissolution of copper can be reduced.

BRIEF DESCRIPTION OF THE DRAWINGS The invention will be described more fully hereinafter with reference to the accompanying drawings, It should be understood, however, that the invention is not limited thereto and that various changes and modifications may be made without departing from the spirit and scope of the invention.

Unless otherwise defined, all technical and scientific terms have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention is merely intended to effectively describe a specific embodiment and is not intended to limit the invention.

Also, the singular forms as used in the specification and the appended claims are intended to include the plural forms as well, unless the context clearly indicates otherwise.

(1) Etching additive for controlling the etching rate

Hereinafter, the etching additive of the present invention will be described.

One aspect of the etch additive of the present invention is

(A) any one or a mixture of two or more selected from inorganic acids, basic hydroxides and alcohols,

(B) at least one compound selected from triazole-based compounds, tetrazole-based compounds, imidazole-based compounds and thiazole-based compounds,

(C) a polymeric amine compound and

(D) an amine-based compound.

In one embodiment of the present invention, (A) any one or two or more selected from inorganic acids, basic hydroxides and alcohols serves to maintain the dispersibility of the etching additive in the etchant. In addition, it has a role of improving the stability of the etching rate and the stability of the dissolution of the additive, and more specifically, the stability of the metal or metal alloy, more specifically, the dissolution bonding stability between the copper ion and the additive during etching of the copper or copper alloy, It is possible to prevent it from adhering to the surface. Although the content is not limited, it may be 60 to 99 wt%, more preferably 65 to 95 wt%, of the total etching additive content. And is suitable for expressing the etching rate required in the above range.

The inorganic acid may be any one or a mixture of two or more selected from sulfuric acid, nitric acid, phosphoric acid, hydrochloric acid, hydrofluoric acid, boric acid and carbonic acid, but is not limited thereto.

The basic hydroxide may be any one or a mixture of two or more selected from sodium hydroxide, potassium hydroxide, barium hydroxide, ammonium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, sodium carbonate and potassium carbonate, It does not.

The alcohols are selected from the group consisting of ethanol, methanol, isobutyl alcohol, benzyl alcohol, isopropyl alcohol, butanol, pentanol, hexanol, heptanol, octanol, isobutyl alcohol, propanol, diacetone alcohol, Propanol, propanol, propanol, propyl alcohol, furfuryl alcohol, diol, 3-chloro-1,2-propanediol, triol, Propanol, 3-bromo-1-propanol, 3-iodo-1-propanol, 4-chloro-1 Butane, n-butanol, n-pentanol, n-hexanol and 2-chloroethanol, and the like, but is not limited thereto.

In one embodiment of the present invention, any one or a mixture of two or more selected from the above (B) triazole-based compounds, tetrazole-based compounds, imidazole-based compounds and thiazole-based compounds has a role of inhibiting etching and forming an organic film. In one embodiment of the etching additive of the present invention, any one or a mixture of two or more selected from the above-mentioned triazole-based compounds, tetrazole-based compounds, imidazole-based compounds and thiazole-based compounds is used. By using these alone or in combination, It has been found that a strong and uniform organometallic modified coating can be formed by combining them with copper ions or the like which are eluted or oxidized during etching of a metal or a metal alloy, more specifically, copper and a copper alloy, It has been found that the ratio of the top portion and the bottom portion of the circuit can be made close to 1: 1 even in the mixed use. The content thereof is not limited, but may be 0.01 to 30 wt%, more preferably 0.1 to 10 wt%, of the total etching additive content. The etching rate can be maintained while exhibiting an intended etching suppressing effect in the above content range.

The triazole type compound is specifically exemplified by 1,2,3-triazole, 1,2,4-triazole, 5-phenyl-1,2,4-triazole, Amino-1,2,4-triazole, 1,2,3-benzotriazole, 1-methyl-benzotriazole, tolyltriazole, sodium benzotriazole, tolythriazol sodium 3-amino-5-methyltriazole, 3-amino-5-ethyltriazole, 3,5-diamino-1,2,4-triazole, 3-amino-1,2,4-triazole-5-carboxylic acid, 5-amino-1,2,3,4-thiatriazole, and the like, or a mixture of two or more thereof. If necessary, derivatives of triazole-based compounds may be used, but the present invention is not limited thereto.

The tetrazole-based compound is specifically exemplified by 1 H-tetrazole, 5-amino-1H-tetrazole, 5-amino-1H-tetrazole monohydrate, -Tetrazole, 5-mercapto-1H-tetrazole, 1-phenyl-5-mercapto-1H-tetrazole, 1-cyclohexyl-5-mercapto- Aminotetrazole, 1-methyl-5-aminotetrazole, 1-ethyl-5-aminotetrazole, Aminoethyl) tetrazole, and the like, or a mixture of two or more thereof. If necessary, derivatives of tetrazole compounds may be used, but the present invention is not limited thereto.

The imidazole compound is specifically exemplified by imidazole, ethylimidazole, methylimidazole, 2-ethylimidazole, 2-methylimidazole, 2-butylimidazole, (Aminophenyl) imidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, benzimidazole, Benzoimidazole, 2-methylbenzoimidazole, 2-methylbenzoimidazole, 5-amino benzoimidazole, 5-amino benzoimidazole, Aminodiazole-4-carbonitrile, 4-phenylimidazole-2-amine, 2- (aminomethyl) imidazole dihydrochloride, 2- (aminomethyl) benzimidazole dihydrochloride, 4- Imidazole-5-carbonitrile, 2-isopropylimidazole, 2-propylimidazole, 2,4-dimethylimidazole, 2-aminoimidazole, mercaptobenzimidazole 2- Benzoimidazoles such as benzyl imidazole, benzyl imidazole, benzyl imidazole, benzyl imidazole, benzoimidazole benzimidazole, 2-chlorobenzyl benzimidazole, 2-bromophenyl benzimidazole, 2-chlorophenyl benzimidazole, 2-bromoethyl phenyl benzimidazole, 2-undecyl-4-methylimidazole, and the like, or a mixture of two or more thereof. If necessary, a derivative of an imidazole-based compound may be used, but the present invention is not limited thereto.

Specific examples of the thiazole-based compound include thiazole, 2-ethylthiazole, 2,4-dimethylthiazole, 4,5-dimethylthiazole, 2-aminothiazole, , 2-aminomethyl thiazole, 2-amino-4-methyl thiazole, 1,2-thiazole, 1,3-thiazole, benzothiazole, Aminobenzothiazole, 2-mercaptobenzothiazole, 2-isopropyl-4-methylthiazole, 5-formyl-4-methylthiazole and 5-amino-3H-thiazole. One or a mixture of two or more may be used. If necessary, derivatives of thiazole-based compounds may be used, but the present invention is not limited thereto.

In one embodiment of the present invention, the (C) polymeric amine compound is used together with the azole compound (B) to serve as an auxiliary agent for forming an organometallic modified coating. Compared with the use of a common primary to quaternary amine compound alone, the present invention can improve the undercut, dent, straightness, etc. by forming the organometallic modified coating more firmly by using a polymeric amine compound. But may be, for example, a water-soluble polymer having, for example, a polyamine chain or a cationic group. The weight average molecular weight may be not less than 300 g / mol, and may be 300 to 100,000 g / mol. More specifically, for example, a quaternary ammonium salt type styrene polymer, a quaternary ammonium salt type aminoalkyl (meth) acrylate polymer, a quaternary ammonium salt type diallylamine polymer, a quaternary ammonium salt type diallylamine-acrylamide A quaternary ammonium salt type polymer such as a copolymer, a polymer of a polyethyleneimine, a polyalkylene polyamine, a salt of an aminoalkyl acrylamide, and a cationic cellulose derivative. Examples of the salt include hydrochloride and the like.

In one embodiment of the present invention, the polymeric amine compound is preferable because it uses polyethyleneimines to form an organic coating, so that the straight portion of the bottom portion can be further improved in the top portion, and the weight average molecular weight is 300 to 70,000 g / mol But is not limited thereto. Commercialized examples include, but are not limited to, NIPPON SHOKUBAI EPOMIN. The " weight average molecular weight " is a value obtained in terms of polyethylene glycol by gel permeation chromatography analysis.

The polyethyleneimine exists in both linear and branched forms and is one of the polymers having cationic properties because it contains various amine groups such as primary amine, secondary amine and tertiary amine. The present invention is advantageous in that the inclusion of the polyethyleneimine in the etching additive further improves the effect of forming the organometallic modified film so that the etching rate in the horizontal direction at the time of etching is controlled to be slow so that an excellent fine pitch pattern etching process can be performed do.

The polymeric amines may be used in an amount of 0.0001 to 5 wt%, preferably 0.001 to 5 wt%, based on the total amount of the etching additive, but are not limited thereto. It is sufficient to have the role of forming the aimed organometallic modified coating in the above range.

In one embodiment of the present invention, the (D) amine compound is used together with the azole compound (B) to maintain the etching rate and to function as an organometallic modified film-forming auxiliary. In addition, the etching rate can be precisely controlled by making the organometallic film formation uniform and constant during etching of copper or copper alloy. When the etching rate is constant and precisely controlled, the amount of the organic metal modified coating formed on the copper surface and the amount of the organic coating removed by the etching solution can be maintained at a constant level. Thus, a fine circuit having a uniform circuit shape can be formed. Specific examples include, but are not limited to, ethylenediamine, trimethylenediamine, tetramethylenediamine, diethanolamine, triethylamine, triethanolamine, ethylamine, methylamine, hexylamine, isobutylamine, tert-butylamine Such as tributylamine, dipropylamine, dimethylamine, monoethanolamine, methyldiethanolamine, diethanolamine, N-methylethylenediamine, triethylenetetraamine, diethylenetriamine and tris (2-aminoethyl) amine , Or a mixture of two or more thereof. The content thereof is not limited, but it may be 0.0001 to 5% by weight, preferably 0.001 to 5% by weight, of the entire etching additive. By using in the above-mentioned range, a uniform and fine circuit can be formed.

(2) The etching solution

Hereinafter, the etching solution of the present invention will be described.

In one embodiment of the present invention, the etching solution may be an etching solution of iron chloride, copper chloride, hydrogen peroxide, sulfuric acid, or an alkali etching type.

The etching solution of the present invention may contain 1 to 40% by weight, more preferably 1 to 30% by weight, of the total amount of the etching additive, but is not limited thereto. The etching rate control and the formation of the organometallic modified film are excellent in the above range.

In one aspect of the present invention, when the etchant is an etchant of copper or a copper alloy, it may include the etchant and a metal ion source and water.

More specifically, it may contain 1 to 40% by weight of the etching additive, 1 to 50% by weight of a metal ion source, and residual water. The metal ion source may be at least one selected from the group consisting of cuprous chloride, cuprous oxide, cupric chloride, cupric oxide, copper powder, copper sulfate, copper bromide, copper salt of organic acid, copper hydroxide and metal hydrate But is not limited thereto. In the present invention, when copper or copper alloy is used for etching, the use of cupric chloride has a fast etching rate. The content of the metal ion source is preferably 1 to 50% by weight, more preferably 5 to 40% by weight based on the total weight of the etchant. The etch rate is high and the dissolution stability of the metal is excellent in the above range.

In one embodiment of the etching solution of the present invention, the water is used for dissolving each component to adjust the concentration. The water may be used at different concentrations depending on the thickness of the substrate and the kind of the metal. The water is preferably ionic substances such as ion-exchange water, pure water, and ultrapure water, or water from which impurities are removed.

Other components may be added to the etching solution of the present invention to such an extent as not to interfere with the effects of the present invention. For example, a surfactant, a dispersion stabilizer, a defoaming agent and the like may be added.

The etching solution may be blended so that each component has a predetermined concentration at the time of use, or it may be diluted immediately before use with preparing a concentrated solution.

The etchant may be treated at 25 to 50 ° C. for 30 to 120 seconds in order to realize the productivity and etch factor. The treatment temperature and time may vary depending on the type and thickness of the substrate, and thus the present invention is not limited thereto. As the treatment method, both spraying and immersion methods can be used, and in the case of spraying method, the pressure is preferably 0.05 to 0.3 MPa.

The etching solution of the present invention can be particularly useful for the production of a printed wiring board which forms a wiring pattern of copper by etching. For example, an etching resist is formed on a copper foil on an insulating substrate, an electroless copper plating film, an electrolytic copper plating film, a copper sputtering film, or a multilayer film thereof, and copper of a portion not covered with the etching resist is etched, This is useful when forming a pattern.

(3) Method of manufacturing wiring

Next, a method of forming a wiring of the present invention will be described.

The method for forming a wiring of the present invention is characterized in that etching is performed using an etching solution containing the above-mentioned etching additive of the present invention in a method of forming a wiring for etching a portion of the metal layer not covered with an etching resist. Thus, by controlling the etching rate, a copper wiring having excellent linearity can be formed.

A specific embodiment of the method for manufacturing a wiring of the present invention is a method for manufacturing a wiring by etching copper or a copper alloy, wherein a portion of the copper layer on the electrical insulating material, which is not covered with the etching resist, is etched using the etching solution, Thereby forming a wiring.

The etching solution of the present invention can be used by a dipping method, a spraying method, or the like. When the spraying method is employed, the pressure is preferably 0.05 to 0.3 MPa. It is possible to effectively perform etching in the above range.

The etchant is not limited, but it is preferable to treat at 25 to 50 ° C for 30 to 120 seconds in order to realize the productivity and the etching factor. The treatment temperature and time may vary depending on the type and thickness of the substrate, and thus the present invention is not limited thereto.

Hereinafter, the present invention will be described in more detail based on examples and comparative examples. However, the following examples and comparative examples are merely examples for explaining the present invention in more detail, and the present invention is not limited by the following examples and comparative examples.

(Test substrate used)

An etching resist pattern was formed on the copper foil having a thickness of 12 占 퐉. At this time, the etching resist pattern was a pattern in which a resist pattern of line / space (L / S) = 10 μm / 12 μm and a resist pattern of line / space (L / S) = 18 μm / 22 μm were mixed.

(Etching condition)

Etching was carried out using a linear nozzle (product name: QMVV11002, product of Spaying system) at a spray pressure of 0.15 MPa and a treatment temperature of 45 캜 for 60 seconds. The etching processing time was set to a time point at which the bottom width of the copper wiring after etching in the resist pattern area of line / space (L / S) = 10 mu m / 12 mu m reached 6 to 9 mu m. After the etching, the substrate was washed with water and dried, and the following evaluations were carried out.

(Image measurement by microscope)

A part of each of the etched substrates was cut, fixed and cured to a room temperature curable acrylic resin, and polished so that the cross section of the copper wiring could be observed. Then, the width of the top portion of the copper wiring and the width of the bottom portion of the copper wiring were measured according to the image measurement of the microscope. In addition, the etching factor in the resist pattern area of L / S = 10 mu m / 12 mu m was calculated by the following formula.

Etching factor = 2 x Circuit thickness (占 퐉) / {Bottom width (占 퐉) of copper wiring - Top width (占 퐉) of copper wiring}

(Evaluation of whether or not micro-etching has occurred)

Each of the etched substrates was immersed in a 3 wt% aqueous solution of sodium hydroxide at a treatment temperature of 40 캜 for a treatment time of 60 seconds to remove the etching resist. Then, the film was dipped in hydrochloric acid (hydrogen chloride concentration: 7 wt%) at a treatment temperature of 25 ° C for 30 seconds to remove the oxide film. Then, on the surface of the test substrate, an image of the copper wiring portion after etching of the resist pattern area of L / S = 10 mu m / 12 mu m was taken with a microscope and the wiring width of the copper wiring portion was image-measured. The existence of the unetched portion was confirmed by observation with a metal microscope.

[Production Examples 1 to 9]

An etching additive having the composition shown in Table 1 below was prepared.

Manufacturing example ingredient Content (% by weight) Production Example 1 Hydrochloric acid 80 5-Amino-1H-tetrazole 15 2-methylimidazole 4 Monoethanolamine 0.9 Polyethyleneimine 0.1 Production Example 2 Hydrochloric acid 80 1,2,3-benzotriazole 10 2-methylimidazole 8 N-methylethylenediamine 1.95 Polyethyleneimine 0.05 Production Example 3 Hydrochloric acid 80 Benzimidazole 10 5-amino-1,2,3,4-thiatriazole 8 Diethanolamine One  Polyethyleneimine One Production Example 4 Hydrochloric acid 80 Benzothiazole 15 5-amino-1,2,4-triazole 4 Ethylenediamine 0.9 Polyethyleneimine 0.1 Production Example 5 Hydrochloric acid 85 5-Amino-1H-tetrazole 8 Triethanolamine One Polyethyleneimine One Production Example 6 Hydrochloric acid 100 Production Example 7 Hydrochloric acid 90 5-Amino-1H-tetrazole 10 Production Example 8 Hydrochloric acid 90 1,2,3-benzotriazole 10 Production Example 9 Hydrochloric acid 90 Benzimidazole 10

In Table 1, polyethyleneimine was EPOMIN SP-018 manufactured by NIPPON SHOKUBAI INC. Having a weight average molecular weight of 1,800 g / mol.

[Examples 1 to 45]

An etching solution was prepared with the compositions shown in Table 2 below, and etching was performed under the above conditions, and the respective items were evaluated by the above evaluation method.

[Comparative Examples 1 to 4]

An etching solution was prepared with the compositions shown in Table 2 below, and etching was performed under the above conditions, and the respective items were evaluated by the above evaluation method.

Content (% by weight) Top / Bottom
Width (탆) Etch factor Etching occurs on / off Etching additive Cupric chloride dihydrate water Kinds content Example 1 Production Example 1 10 5 85 9.0 / 9.6 26.6 radish Example 2 Production Example 1 20 5 75 8.7 / 9.1 40.0 radish Example 3 Production Example 1 30 5 65 8.6 / 9.0 40.0 radish Example 4 Production Example 1 10 20 70 8.7 / 9.3 26.6 radish Example 5 Production Example 1 20 20 60 8.0 / 8.5 32.0 radish Example 6 Production Example 1 30 20 50 7.8 / 8.3 32.0 radish Example 7 Production Example 1 10 40 50 8.5 / 9.1 26.6 radish Example 8 Production Example 1 20 40 40 7.6 / 8.0 26.6 radish Example 9 Production Example 1 30 40 30 6.8 / 7.5 22.8 radish Example 10 Production Example 2 10 5 85 8.9 / 9.5 22.6 radish Example 11 Production Example 2 20 5 75 8.5 / 8.9 40.0 radish Example 12 Production Example 2 30 5 65 8.3 / 8.8 32.0 radish Example 13 Production Example 2 10 20 70 8.3 / 9.0 22.8 radish Example 14 Production Example 2 20 20 60 7.9 / 8.4 32.0 radish Example 15 Production Example 2 30 20 50 7.7 / 8.2 32.0 radish Example 16 Production Example 2 10 40 50 8.5 / 9.3 20.0 radish Example 17 Production Example 2 20 40 40 7.5 / 8.0 32.0 radish Example 18 Production Example 2 30 40 30 6.9 / 7.5 26.6 radish Example 19 Production Example 3 10 5 85 8.5 / 9.2 22.8 radish Example 20 Production Example 3 20 5 75 8.3 / 8.9 26.6 radish Example 21 Production Example 3 30 5 65 8.3 / 8.8 32.0 radish Example 22 Production Example 3 10 20 70 8.3 / 9.1 22.8 radish Example 23 Production Example 3 20 20 60 8.0 / 8.5 32.0 radish Example 24 Production Example 3 30 20 50 7.9 / 8.4 32.0 radish Example 25 Production Example 3 10 40 50 8.2 / 9.1 17.7 radish Example 26 Production Example 3 20 40 40 7.0 / 7.7 22.8 radish Example 27 Production Example 3 30 40 30 6.9 / 7.6 22.8 radish Example 28 Production Example 4 10 5 85 8.4 / 9.2 20.0 radish Example 29 Production Example 4 20 5 75 8.0 / 8.6 26.6 radish Example 30 Production Example 4 30 5 65 7.8 / 8.5 22.8 radish Example 31 Production Example 4 10 20 70 8.1 / 9.0 17.7 radish Example 32 Production Example 4 20 20 60 7.8 / 8.5 22.8 radish Example 33 Production Example 4 30 20 50 7.5 / 8.2 22.8 radish Example 34 Production Example 4 10 40 50 8.2 / 9.1 17.7 radish Example 35 Production Example 4 20 40 40 7.0 / 7.7 22.8 radish Example 36 Production Example 4 30 40 30 6.8 / 7.6 20.0 radish Example 37 Production Example 5 10 5 85 8.4 / 9.1 22.8 radish Example 38 Production Example 5 20 5 75 8.2 / 8.7 32.0 radish Example 39 Production Example 5 30 5 65 8.2 / 8.7 32.0 radish Example 40 Production Example 5 10 20 70 8.2 / 8.9 26.6 radish Example 41 Production Example 5 20 20 60 7.8 / 8.3 32.0 radish Example 42 Production Example 5 30 20 50 7.9 / 8.4 32.0 radish Example 43 Production Example 5 10 40 50 7.9 / 8.6 22.8 radish Example 44 Production Example 5 20 40 40 7.0 / 7.6 26.6 radish Example 45 Production Example 5 30 40 30 7.1 / 7.7 26.6 radish Comparative Example 1 Production Example 6 20 40 40 - - radish Comparative Example 2 Production Example 7 20 40 40 5.5 / 10.2 3.4 U Comparative Example 3 Production Example 8 20 40 40 6.3 / 10.3 4.0 U Comparative Example 4 Production Example 9 20 40 40 - - U

As shown in Table 2, in Examples 1 to 45 using the etching additive of the present invention, it was found that the ratio of the top portion to the bottom portion was close to 1: 1 and the etching factor was 10 or more. On the other hand, in the case of Comparative Examples 1 to 4 in which the etching additive of the present invention was not used, it can be seen that the circuit is eliminated or the width of the bottom portion is wider than that of the top portion, and that the etch phenomenon occurs and the etching factor is less than 5 there was.

Claims (7)

(A) any one or a mixture of two or more selected from inorganic acids, basic hydroxides and alcohols,
(B) at least one compound selected from triazole-based compounds, tetrazole-based compounds, imidazole-based compounds and thiazole-based compounds,
(C) polyethyleneimine and
(D) a polymerization initiator selected from the group consisting of ethylenediamine, trimethylenediamine, tetramethylenediamine, diethanolamine, triethylamine, triethanolamine, ethylamine, methylamine, hexylamine, isobutylamine, tert-butylamine, tributylamine, dipropylamine , A mixture of one or more selected from the group consisting of dimethylamine, monoethanolamine, methyldiethanolamine, diethanolamine, N-methylethylenediamine, triethylenetetramine, diethylenetriamine and tris (2-aminoethyl) An amine-based compound. delete The method according to claim 1,
(A) 60 to 99% by weight of any one or a mixture of two or more selected from inorganic acids, basic hydroxides and alcohols, (B) any one selected from triazole type compounds, tetrazole type compounds, imidazole type compounds and thiazole type compounds 0.01 to 30% by weight of at least two mixtures, (C) 0.0001 to 5% by weight of polyethyleneimine and (D) 0.0001 to 5% by weight of an amine compound. An etchant for producing interconnects comprising an etchant additive selected from the group consisting of the following: 5. The method of claim 4,
And 1 to 40% by weight of the etchant additive. A method of manufacturing a wiring by etching a metal or metal alloy,
Wherein a portion of the metal layer on the electrical insulating material that is not covered with the etching resist is etched with the etching solution described in Claim 4 to form a wiring. The method according to claim 6,
Wherein the metal is copper.