KR101298766B1 - Etching solution composites for nickel, chrome, and/or nickel-chrome alloy and etching method using the etching solution composites - Google Patents

Abstract

 Etching solution compositions of nickel, chromium, or nickel-chromium alloys are disclosed. The etching solution composition of nickel, chromium, or nickel-chromium alloy according to an embodiment of the present invention is an etching solution consisting of at least one of an oxidizing agent, a cysteine derivative sulfur compound and a water-soluble mercapto organic material composed of at least one solution of sulfuric acid and hydrogen peroxide. Inhibitors, one or more surfactants, and stabilizers composed of at least one substance from organic phosphoric acid and organic acids including multiple charged phosphorus.

Description

Etching solution composites for nickel, chrome, and / or nickel-chrome alloy and etching method using the etching solution composites}

FIELD OF THE INVENTION The present invention relates to etching solution composites, and more particularly to etching used to etch nickel, Ni, chrome, Cr and / or nickel-chrome alloys. It relates to a solution composition and an etching method using the same.

Printed circuit boards (PCBs) are mounted with various electrical and electronic devices, such as active devices such as semiconductor chips, as well as passive devices such as resistors, conductors, and coils. And a printed circuit board (PCB) is formed with a wiring (circuit) for electrically connecting such electrical and electronic elements. In recent years, as the advancement of high performance, high speed, and miniaturization of electronic products, the integration of electrical and electronic devices such as high density is rapidly increasing, and the response speed of the circuit is required rapidly. Wiring must be made of a material with low resistance. The most widely used metal material for wiring is copper (Cu). Copper has a lower electrical resistance than other metals and thus has excellent electrical conductivity.

In the conventional printed circuit board (PCB), a hard board is used, but recently, a flexible printed circuit board (flexibe PCB) is widely used. The flexible printed circuit board is not only flexible but also thin and light because the substrate has a film shape. Such flexible printed circuit boards are widely used in various information communication products that are miniaturized and lightweight, such as hard disk drives, mobile phones, digital cameras, and LCD (LCD) drives. Therefore, considering the current trend of information and communication technology, the demand for information communication products using flexible printed circuit boards is expected to increase steadily.

The flexible substrate of the flexible printed circuit board is made of a resin material such as polyimide. By the way, the resin forming the flexible substrate is not only good adhesion to copper, but also has a disadvantage of poor corrosion resistance and movement inhibiting properties. Therefore, in order to extend the durability of copper as wiring and to improve electrical characteristics and adhesion, an adhesive pattern or a buffer pattern formed of another material is interposed between the copper wiring and the flexible substrate.

Materials widely used as adhesive patterns or buffer patterns are alloy materials of nickel, chromium, and / or nickel-chromium. The adhesive pattern may be formed using a deposition process such as nickel and a selective etching process. More specifically, a metal seed layer or a base metal layer having a thickness of about 10 to 150 micrometers is formed on the flexible substrate using nickel, chromium, and / or nickel-chromium alloy materials by using a deposition process of a metal material such as sputtering. Then, a wiring circuit is formed of copper on the metal seed layer. The wiring circuit can be formed only on a desired portion on the metal seed layer using an electroplating method or the like. The metal seed layer portion of the portion where the wiring circuit is not formed is selectively etched and removed to form a wiring circuit having an adhesive pattern or a buffer pattern formed of nickel, chromium, and / or nickel-chromium alloy on the flexible substrate. You can do it.

For the selective etching of metal seed layers formed of nickel, chromium, and / or nickel-chromium alloys, an etchant mainly composed of ferric chloride and an etchant mainly composed of cerium ammonium nitrate (IV) are widely used. However, the etching solution containing ferric chloride as a main component has a poor selectivity of the metal to be etched, so that the copper layer constituting the wiring circuit as well as the nickel, chromium, and nickel-chromium alloys are etched. The etchant mainly composed of cerium ammonium nitrate (IV) has excellent etching performance for nickel, chromium, and nickel-chromium alloys, but also has poor etching selectivity, thus damaging copper. When copper is etched together during the etching of the metal seed layer, the width of the wiring decreases, thereby increasing the resistance or, in severe cases, disconnection. In some cases, etched copper may adhere onto the metal seed layer, resulting in a short circuit. As a result, the electronic products including the flexible printed circuit board manufactured according to the conventional method have a problem of low productivity, low reliability and stability.

One problem to be solved by the present invention is an etching solution composition of nickel, chromium, nickel-chromium alloys having excellent protection against copper and excellent etching characteristics for nickel, chromium, and nickel-chromium alloys, and an etching method using the same. To provide.

Another object of the present invention is to provide an etching solution composition of nickel, chromium, nickel-chromium alloy and etching method using the same which can be used to form a copper wiring circuit having excellent electrical characteristics on a flexible substrate.

The etching solution composition of nickel, chromium, or nickel-chromium alloy according to an embodiment of the present invention for solving the above problems is in the oxidizing agent, cysteine derivative sulfur compound and water-soluble mercapto organic material composed of at least one solution of sulfuric acid and hydrogen peroxide An etch inhibitor composed of at least one material, one or more surfactants, and a stabilizer composed of at least one of an organic acid and an organic acid comprising multiple charged phosphorus.

 According to an aspect of the embodiment, the sulfuric acid may include 2 to 25% by weight based on the etching solution composition, the hydrogen peroxide may include 0.1 to 5% by weight based on the etching solution composition.

And the etching inhibitor is based on 1 liter of the etching solution composition N-ethylcysteine (N-ethylcysteine) 0.001g ~ 2.0g, N-propylcysteine (N-propylcysteine) 0.001g ~ 2.0g, N-isopropylcysteine ( N-Isopropylcysteine) 0.001g to 3.0g, N-Isobutylcysteine 0.001g to 3.0g, N-Cyclohexylcysteine 0.002g to 2.0g, N- (cyclohexylmethyl) 0.001 g to 2.0 g cysteine (N- (Cyclohexylmethyl) cysteine), 0.001 g to 1.0 g S- (tert-Butylthio) -L-cysteine, cysteine N-carbodithioic acid (cysteine) N-carbodithioic acid potassium salt) 0.001 g to 1.0 g, N, N-dimethyl-dithiocarbamyl propyl sulfonic acid 0.001 g to 1.0 g, ethyl-dithiocarbamyl-propyl sulfonic acid 0.001 g to 1.0 g, and bis -(Sodium sulfopropyl) -disulfide may be composed of one or more compounds selected from the group consisting of 0.001g to 1.0g. In addition, the water-soluble mercapto organic compounds are N-alkyl (C1-C5), N-dialkyl (C1-C5), N-isoalkyl (C1-C5), and N-cycloalkyl as cysteine derivative water-soluble mercapto organic compounds. It may include derivatives containing at least one selected from the group consisting of (C3 ~ C8).

According to another aspect of the embodiment, the surfactant is 0.0001g to 0.05g cross-linked polyamide (Mn = 1,000 ~ 400,000) based on 1 liter of the etching solution composition, polypropylene glycol ethylene oxide (Mn = 1,500 to 100,000) 0.0001 g to 0.01 g, polyvinylpyrrolidone (Mn = 5,000 to 100,000) 0.0001 g to 0.1 g, polyvinyl alcohol (Mn = 1,000 to 200,000) 0.0001 g to 0.005 g, polyalkyl beta-naphthol (Mn = 5,000-100,000) 0.0001 g to 0.005 g, poly (diallyldimethylammonium chloride) 0.0001 g to 0.5 g, steaalconium chloride 0.0001 g to 0.001 g, cetyltrimethylammonium chloride 0.0001 g to 0.03 g, (3 -Chloro-2-hydroxypropyl) trimethylammonium chloride 0.0001g to 0.03g, octyltrimethylammonium chloride 0.0001g to 0.03g, and benzyldimethyl (2-hydroxyethyl) ammonium chloride 0.001g to 0.03g Consisting of one or more compounds It can be. And the stabilizer is based on 1 liter of the etching solution composition bis (hexamethylenetriamine penta (methylene phosphonic acid) 1g ~ 10g, diethylenetriamine penta (methylene phosphonic acid) 1g ~ 10g, ethylenediamine tetra ( Methylene phosphonic acid) 1 g to 10 g, nitrilotriacetic acid 0.1 g to 5 g, ethylenediaminetetraacetic acid 0.1 g to 5 g, toluene sulfonic acid 1 g to 10 g, tartaric acid 0.1 g to 10 g, and citric acid 0.1 g to 5 g It may include one or more compounds.

An etching method according to an embodiment of the present invention for solving the above problems is a substrate having a metal seed layer formed of nickel, chromium, or nickel-chromium alloy and a wiring circuit of a predetermined pattern formed of copper on the metal seed layer. Preparing and selectively etching the nickel, chromium, or nickel-chromium alloy in a portion where the wiring circuit is not formed by immersing the substrate in an etching solution composition according to an embodiment of the present invention described above. It includes.

Using the etching solution composition which concerns on this invention, the nickel, chromium, or nickel-chromium alloy which forms a metal seed layer with respect to copper which is a main metal which comprises a wiring circuit can be etched rapidly. Therefore, since unnecessary metal seed layers can be removed quickly, not only productivity is improved but also high selectivity to copper does not cause abnormal precipitation of copper. As a result, since the electrical resistance of the printed circuit board on which the etching process with respect to the metal substrate board is completed does not increase or cause disconnection, a printed circuit board having excellent electrical characteristics can be manufactured.

1 is a flowchart showing an etching method according to an embodiment of the present invention.
2A and 2B are scanning electron microscopes (SEMs) for wiring circuits before and after etching a nickel, chromium, or nickel-chromium alloy using an etching solution composition according to an embodiment of the present invention, respectively. It is a photograph.
3A and 3B are SEM photographs of wiring circuits when a conventional etching solution composition containing ferric chloride and an etching solution using an etching solution composition according to Experimental Example 1 of the present invention are used.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. The terms used are terms selected in consideration of the functions in the embodiments, and the meaning of the terms may vary depending on the user, the intention or custom of the operator, and the like. Therefore, the meaning of the terms used in the following embodiments is defined according to the definition when specifically defined in this specification, and unless otherwise defined, it should be interpreted in a sense generally recognized by those skilled in the art.

In order to improve the adhesion between the substrate, in particular, a flexible substrate formed of a resin material such as polyimide and the like, and a low resistance, the adhesion pattern or the buffer pattern formed of nickel, chromium, or nickel-chromium alloy is used. Used. The printed circuit board having the adhesive pattern or the buffer pattern interposed between the substrate and the wiring circuit forms a metal seed layer or a base metal layer on the substrate, and then uses a portion where the wiring circuit is not formed, that is, a wiring circuit as an etching mask. Exposed nickel, chromium, or nickel-chromium alloys may be formed by etching. In this case, a wet etching process is generally used. In order to manufacture a printed circuit board having excellent electrical characteristics, a compound having excellent etching characteristics for nickel, chromium, and nickel-chromium alloys, but which does not etch copper well, is used. It should be used as an etching solution.

According to an embodiment of the present invention, a composition including an oxidizing agent, an etching inhibitor, a surfactant, and a stabilizer of a metal is used as an etching solution of such nickel, chromium, or nickel-chromium alloy. More specifically, the etching solution composition comprises an etch inhibitor composed of at least one solution of sulfuric acid and hydrogen peroxide, a cysteine derivative sulfur compound, and at least one substance of a water soluble mercapto organic material, one or more surfactants, and multiple charged phosphorus. It comprises a stabilizer composed of at least one material of an organic phosphoric acid and an organic acid comprising a.

The oxidant of the metal may be composed of at least one solution of hydrogen peroxide and phosphorus sulfate which is an inorganic acid. If the amount of sulfuric acid contained in the etching solution is too high or the concentration is too high, the oxidation power to the metal is strong, so that the etching rate of nickel, chromium, nickel-chromium alloy may increase, but at the same time, corrosion of copper may occur. Conversely, if the amount of sulfuric acid contained in the etching solution is too small or the concentration is too low, the oxidizing power for the metal is weakened and the etching rate may be very slow. As a powerful oxidant to control the etch rate of nickel, chromium and nickel-chromium alloys, hydrogen peroxide can be used together with or alone with sulfuric acid.Too much hydrogen peroxide or high concentrations, like sulfuric acid, can cause copper to form a wiring circuit. Non-uniform etching due to bubbles as well as erosion can occur, and a low or low concentration of hydrogen peroxide can significantly reduce the etching rate of nickel, chromium and nickel-chromium alloys. Therefore, according to an embodiment of the present invention, the preferred use range of sulfuric acid based on the etching solution composition is 2 to 25% by weight, more preferably 10 to 20% by weight, the preferred range of hydrogen peroxide is 0.1 to 5% by weight More preferably, it is 0.3-3 weight%.

The etch inhibitor performs a function of suppressing etching to the copper forming the wiring circuit. As the etching inhibitor, any one of a cysteine derivative sulfur compound and a water-soluble mercapto organic material may be used alone or in combination. When the amount of the etching inhibitor added to the etching solution is too large, a problem may occur that erosion occurs in the base metal layer under the copper layer constituting the wiring circuit. On the other hand, when the amount of the etching inhibitor contained in the etching solution is too small, there is a problem that erosion of the copper itself constituting the wiring circuit occurs. Therefore, based on 1 liter of the etching solution composition according to the embodiment of the present invention, the type and preferable use range of the cysteine derivative sulfur compound and / or the water-soluble mercapto organic substance added thereto are 0.001 g to 2.0 g N-ethyl cysteine, N-propylcysteine 0.001g to 2.0g, N-isopropylcysteine 0.001g to 3.0g, N-isobutylcysteine 0.001g to 3.0g, N-cyclohexylsteine 0.002g to 2.0g, N- (cyclohexylmethyl Cysteine 0.001g ~ 2.0g, S- (tert-butylthio) cysteine 0.001g ~ 1.0g, cysteine N-carbodithioic acid 0.001g ~ 1.0g can be used alone or in combination, and also N, N-dimethyl Dithiocarbamyl propyl sulfonic acid 0.001 g to 1.0 g, ethyl-dithiocarbamyl-propyl sulfonic acid 0.001 g to 1.0 g, bis- (sodium sulfopropyl) -disulfide 0.001 g to 1.0 g may be used alone or in combination Can be. Among the above-mentioned water-soluble mercapto organic compounds, the cysteine derivative water-soluble mercapto organic compound synthesized as a starting material is N-alkyl (C1-C5), N-dialkyl (C1-C5), and N-isoalkyl (C1-C). C5), derivatives containing N-cycloalkyl (C3-C8).

Surfactants interact with cysteine derivative sulfur compounds and / or water-soluble mercapto organics, which are etching inhibitors, to broadly inhibit the deposition of copper by etching solutions. In other words, the surfactant helps the action of the etch inhibitor so that the etch inhibitor functions well. If a high concentration of surfactant, ie, a large amount, is added to the etching solution, the selectivity of the etching inhibitor to the metal may be lost, so that etching of the nickel, chromium and nickel-chromium alloys may not occur. On the other hand, when a low concentration of the surfactant is added, that is, a small amount is added, the function of the etching inhibitor may not be fully performed, and erosion of copper constituting the wiring circuit may occur. According to an embodiment of the present invention, such surfactant is 0.0001 g to 0.05 g of cross-linked polyamide (Mn = 1,000 to 400,000), and 0.0001 g to 0.01 of polypropylene glycol ethylene oxide (Mn = 1,500 to 100,000) g, polyvinylpyrrolidone (Mn = 5,000-100,000) 0.0001 g to 0.1 g, polyvinyl alcohol (Mn = 1,000 to 200,000) 0.0001 g to 0.005 g, polyalkyl beta-naphthol (Mn = 5,000 to 100,000) 0.0001 g To 0.005 g, poly (diallyldimethylammonium chloride) 0.0001 g to 0.5 g, steaalconium chloride 0.0001 g to 0.001 g, cetyltrimethylammonium chloride 0.0001 g to 0.03 g, (3-chloro-2-hydroxypropyl) Trimethylammonium chloride 0.0001g to 0.03g, octyltrimethylammonium chloride 0.0001g to 0.03g, benzyldimethyl (2-hydroxyethyl) ammonium chloride 0.001g to 0.03g may be used alone or in combination.

The stabilizer provides uniformity and stability of the liquid by inhibiting decomposition of an oxidizing agent, such as sulfuric acid or hydrogen peroxide, which has a strong oxidizing power, and at the same time capturing the precipitated metal component. That is, the stabilizer also serves as a chelating agent for trapping the precipitated metal component. Such stabilizers may be composed solely or in combination of organophosphoric acid or organic acid components comprising phosphorus with multiple charged centers. When the amount of stabilizing agent and chelating agent is high, that is, when the concentration in the nicking solution is high, the etching rate of nickel, chromium and nickel-chromium alloys may be reduced, and defects may occur in the copper constituting the wiring circuit. have. On the other hand, when less stabilizer and chelating agent are used, long-term liquid stability and uniformity are inferior. According to an embodiment of the present invention, such stabilizers and chelating agents 1 g to 10 g of bis (hexamethylenetriamine penta (methylene phosphonic acid), 1 g to 10 g of diethylenetriamine penta (methylene phosphonic acid), ethylenediamine tetra (Methylene phosphonic acid) 1g to 10g, nitrilotriacetic acid 0.1g to 5g, ethylenediaminetetraacetic acid 0.1g to 5g, toluenesulfonic acid 1g to 10g, tartaric acid 0.1g to 10g, citric acid 0.1g to 5g alone or Or may be used in combination.

The etching solution composition according to the embodiment of the present invention described above may be used as an etching solution for etching a metal base plate formed of nickel, chromium, or nickel-chromium alloy on a substrate. 1 is a flowchart illustrating an etching method according to an embodiment of the present invention, wherein etching is performed using the etching solution composition according to the embodiment of the present invention described above. Referring to FIG. 1, first, a substrate having a metal seed layer formed of nickel, chromium, or a nickel-chromium alloy and a wiring circuit having a predetermined pattern formed of copper on the metal seed layer is prepared (10). Here, there is no restriction | limiting in particular in the process of forming a metal seed layer on a board | substrate, or the process of forming the wiring circuit of a predetermined pattern on a metal seed layer. For example, the metal seed layer may be formed using a conventional metal deposition process such as sputtering, evaporation, or physical vapor deposition. The wiring pattern can be formed using an electroplating method or the like.

The substrate on which the wiring circuit is formed is immersed in the above-described etching solution to perform an etching process for nickel, chromium, or nickel-chromium alloy (20). In this case, the etching solution can be agitated at a predetermined rotational speed, for example, a rotational speed of about 100-300 rpm, and the process temperature can range from about 25 ° C to 35 ° C, which is merely exemplary. When the etching process is performed under the aforementioned process conditions, not only the stability and long life of the etching solution can be ensured, but also nickel, chromium and nickel-chromium alloys can be selectively and quickly etched. In addition, excellent protection of copper, the main metal constituting the wiring circuit, prevents abnormal precipitation of copper, and increases electrical resistance or disconnection. As a result, the printed circuit board formed using the etching method according to the embodiment of the present invention not only shows high productivity but also has excellent reliability of the product.

2A and 2B are scanning electron microscopes (SEMs) for wiring circuits before and after etching a nickel, chromium, or nickel-chromium alloy using an etching solution composition according to an embodiment of the present invention, respectively. It is a photograph. The etching process was performed for 1 minute at room temperature (25 ℃) using the etching solution composition of Experimental Example 1 to be described later, Figure 2b is a SEM photograph taken thereafter. 2A and 2B, the seed layer formed of the nickel-chromium alloy was completely removed by the etching process, and the wiring circuit formed of copper (the right part in FIGS. 2A and 2B) hardly damaged. Able to know.

3A and 3B are SEM photographs of wiring circuits, respectively, when a conventional etching solution composition is used and when etching is performed using an etching solution composition according to an embodiment of the present invention. More specifically, FIG. 3A illustrates a case of etching using an etching solution composition containing ferric chloride as a main component in a conventional etching solution composition, and FIG. 3B illustrates etching using the etching solution composition of Experimental Example 1 described later. to be. Referring to FIGS. 3A and 3B, when nickel, chromium, or nickel-chromium alloys are etched using a conventional etching solution composition mainly composed of ferric chloride as an etching solution, a metal seed layer is formed around the wiring circuit. While there are many residues and damage to the surface of the wiring circuit, when the nickel, chromium, or nickel-chromium alloy is etched using the etching solution composition according to the embodiment of the present invention as an etching solution, the metal seed layer It can be seen that it is completely removed and there is little damage to the wiring circuit.

Next, the characteristic of the etching solution composition which concerns on this invention for an experiment example is demonstrated more concretely. Experimental examples of the present invention described below are merely exemplary, and it is obvious that the technical idea of the present invention is not limited to the specific forms of the experimental examples described below. Therefore, the technical idea of the present invention should be construed to include not only those illustrated in the following experimental examples but also those obvious or modified therefrom.

<Experimental Example 1>

In Experimental Example 1, an etching solution composition of nickel, chromium, and nickel-chromium alloy including the components described in Table 1 below was used. As a substrate, a polyimide film was used, and a base metal layer (or seed layer) having a thickness of about 200 μs was deposited on the upper surface of the polyimide film by sputtering, and a wiring circuit having a predetermined pattern of copper on the base metal layer using plating. Was formed. In the etching step using this etching solution composition, the mixture was stirred at room temperature (25 ° C) at 200 rpm. At the time of etching completion, the time when nickel and chromium were not detected by the measurement by the fluorescent X-ray analyzer was measured. The etching states of the nickel, chromium and nickel-chromium alloys remaining on the copper interface constituting the wiring circuit were confirmed by scanning electron microscopy (SEM). Further, a copper clad laminate (CCL) of 30 mm (width) x 30 mm (length) was immersed in the etching solution composition for 90 seconds, and the degree of copper erosion was confirmed by the weight change before and after.

Referring to Table 1, the time required for etching the nickel-chromium alloy is about 90 seconds, and it can be seen that the etching rate or the etching rate is also about 130 Pa / min or more, which is significantly improved compared with the prior art. And it can be seen that the etching solution composition of Table 1 hardly occurs copper erosion.

<Experimental Example 2>

In Experimental Example 2, an etching solution composition of nickel, chromium, and nickel-chromium alloy containing the components described in Table 2 below was used. As a substrate, a polyimide film was used, and a base metal layer (or seed layer) having a thickness of about 200 μs was deposited on the upper surface of the polyimide film by sputtering, and a wiring circuit having a predetermined pattern of copper on the base metal layer using plating. Was formed. In the etching step using this etching solution composition, the mixture was stirred at room temperature (25 ° C) at 200 rpm. At the time of etching completion, the time when nickel and chromium were not detected by the measurement by the fluorescent X-ray analyzer was measured. The etching states of the nickel, chromium and nickel-chromium alloys remaining on the copper interface constituting the wiring circuit were confirmed by scanning electron microscopy (SEM). Further, a copper clad laminate (CCL) of 30 mm (width) x 30 mm (length) was immersed in the etching solution composition for 110 seconds, and the degree of copper erosion was confirmed by the weight change before and after.

Referring to Table 2, the etching time of the nickel-chromium alloy was about 110 seconds, and the etching rate or etching rate was about 109 Pa / min or more. Able to know. And it can be seen that the copper erosion hardly occurs in the etching solution composition of Table 2.

<Experimental Example 3>

In Experimental Example 3, an etching solution composition of nickel, chromium, and nickel-chromium alloy including the components described in Table 3 below was used. As a substrate, a polyimide film was used, and a base metal layer (or seed layer) having a thickness of about 200 μs was deposited on the upper surface of the polyimide film by sputtering, and a wiring circuit having a predetermined pattern of copper on the base metal layer using plating. Was formed. In the etching step using this etching solution composition, the mixture was stirred at room temperature (25 ° C) at 200 rpm. At the time of etching completion, the time when nickel and chromium were not detected by the measurement by the fluorescent X-ray analyzer was measured. The etching states of the nickel, chromium and nickel-chromium alloys remaining on the copper interface constituting the wiring circuit were confirmed by scanning electron microscopy (SEM). Further, a copper clad laminate (CCL) of 30 mm (width) x 30 mm (length) was immersed in the etching solution composition for 130 seconds, and the degree of copper erosion was confirmed by the weight change before and after.

Referring to Table 3, the etching time of the nickel-chromium alloy is about 130 seconds and the etching rate or etching rate is about 92 GPa / min or more, although the etching rate is lower than that of Experimental Examples 1 and 2, it is significantly improved. It can be seen that. And it can be seen that the copper erosion hardly occurs in the etching solution composition of Table 3.

As described in detail above, the etching solution composition of nickel, chromium, nickel-chromium alloy according to an embodiment of the present invention is at least one of an oxidizing agent, a cysteine derivative sulfur compound and a water-soluble mercapto organic material composed of at least one solution of sulfuric acid and hydrogen peroxide An etch inhibitor composed of a material of, one or more surfactants, and a stabilizer composed of at least one of an organic acid and an organic acid comprising multiple charged phosphorus. Such an etching solution is preferably capable of selectively and quickly etching nickel, chromium, or nickel-chromium alloys with respect to copper when used in a predetermined combination, so that the protection against copper, which is the main metal forming the wiring circuit, is improved. Not only is it excellent, but abnormal precipitation of copper does not occur. Therefore, the printed circuit board formed by using the etching solution composition according to the present invention does not increase the electrical resistance or cause disconnection, so that not only the quality of the product is excellent but also the reliability is excellent. Therefore, it is suitable for use as a printed circuit board of electronic products that are becoming high speed and high performance.

Claims (7)

An oxidizer composed of at least one solution of sulfuric acid and hydrogen peroxide;
Etching inhibitors composed of at least one of cysteine derivative sulfur compounds and water-soluble mercapto organics;
One or more surfactants; And
An etching solution composition comprising an organic phosphoric acid comprising a multi-charged phosphorus and a stabilizer composed of at least one material from among organic acids,
The etching inhibitor is based on 1 liter of the etching solution composition N-ethyl cysteine 0.001g to 2.0g, N-propyl cysteine 0.001g to 2.0g, N-isopropylcysteine 0.001g to 3.0g, N-isobutylcysteine 0.001 g to 3.0 g, N-cyclohexylsteine 0.002g to 2.0g, N- (cyclohexylmethyl) cysteine 0.001g to 2.0g, S- (tert-butylthio) cysteine 0.001g to 1.0g, cysteine N-car Bodithioic acid 0.001 g to 1.0 g, N, N-dimethyl-dithiocarbamyl propyl sulfonic acid 0.001 g to 1.0 g, ethyl-dithiocarbamyl-propyl sulfonic acid 0.001 g to 1.0 g, and bis- (sodium sulfo Propyl) -disulfide, consisting of one or more compounds selected from the group consisting of 0.001 g to 1.0 g,
The surfactant is 0.0001 g to 0.05 g of cross-linked polyamide (Mn = 1,000 to 400,000) based on 1 liter of the etching solution composition, and 0.0001 g to polypropylene glycol ethylene oxide (Mn = 1,500 to 100,000) 0.01 g, polyvinylpyrrolidone (Mn = 5,000 to 100,000) 0.0001 g to 0.1 g, polyvinyl alcohol (Mn = 1,000 to 200,000) 0.0001 g to 0.005 g, polyalkyl beta-naphthol (Mn = 5,000 to 100,000) 0.0001 g to 0.005 g, poly (diallyldimethylammonium chloride) 0.0001 g to 0.5 g, steaalconium chloride 0.0001 g to 0.001 g, cetyltrimethylammonium chloride 0.0001 g to 0.03 g, (3-chloro-2-hydroxypropyl Trimethylammonium chloride 0.0001g to 0.03g, octyltrimethylammonium chloride 0.0001g to 0.03g, and benzyldimethyl (2-hydroxyethyl) ammonium chloride 0.001g to 0.03g Characterized by nickel, chrome, Or an etching solution composition of a nickel-chromium alloy. The method of claim 1,
The sulfuric acid is 2 to 25% by weight based on the etching solution composition, the hydrogen peroxide is etching of nickel, chromium, or nickel-chromium alloy, characterized in that 0.1 to 5% by weight based on the etching solution composition Solution composition. delete The method according to any one of claims 1 to 2,
The water-soluble mercapto organics are N-alkyl (C1-C5), N-dialkyl (C1-C5), N-isoalkyl (C1-C5), and N-cycloalkyl (C3) as cysteine derivative water-soluble mercapto organic compounds. Etching solution composition of nickel, chromium, or nickel-chromium alloy, characterized in that it comprises derivatives containing at least one selected from the group consisting of ~ C8). delete The method according to any one of claims 1 to 2,
The stabilizer is 1 g to 10 g of bis (hexamethylenetriamine penta (methylene phosphonic acid), 1 g to 10 g of diethylenetriamine penta (methylene phosphonic acid), and ethylenediamine tetra (methylene) based on 1 liter of the etching solution composition. Phosphonic acid) 1 g to 10 g, nitrilotriacetic acid 0.1 g to 5 g, ethylenediaminetetraacetic acid 0.1 g to 5 g, toluene sulfonic acid 1 g to 10 g, tartaric acid 0.1 g to 10 g, and citric acid 0.1 g to 5 g Or an etching solution composition of nickel, chromium, or nickel-chromium alloy, characterized in that it comprises a compound or more. Preparing a substrate having a metal seed layer formed of nickel, chromium, or a nickel-chromium alloy and a wiring circuit having a predetermined pattern formed of copper on the metal seed layer; And
Immersing the substrate in the etching solution composition of claim 1 to selectively etch the nickel, chromium, or nickel-chromium alloy in the portion where the wiring circuit is not formed.

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