KR20180093806A - Etchant and fabrication method of metal wiring using the same - Google Patents

Abstract

The present invention relates to an etchant composition and a method for forming metal wiring using the same. More specifically, the present invention relates to the etchant composition used for forming metal wiring by etching a metal film in a predetermined pattern in a process of manufacturing a metal interconnection. The etchant composition comprises: persulfate; fluorine-containing compounds; 4-nitrogen ring compounds; 2-chlorine compounds; water; and the etchant composition having a content ratio of 4-nitrogen ring compound and 2-chlorine compound of 1: 1.4 to 1: 2.

Description

[0001] The present invention relates to an etchant composition and a method for forming a metal wiring using the same,

The present invention relates to an etchant composition, and more particularly, to an etchant composition used for forming a metal interconnection by etching a metal film in a predetermined pattern in a process of manufacturing a metal interconnection.

A thin film transistor (TFT) is used as a circuit for applying a specific signal to each pixel in a liquid crystal display (LCD) or an OLED (Organic Light Emitting Diode) display device. The structure of the thin film transistor is composed of a gate wiring for transmitting a scanning signal, a data wiring for transmitting an image signal, and a pixel electrode connected to the two wirings. The thin film transistor is a device for driving the liquid crystal by changing the voltage applied to the gate electrode and the source / drain electrode. The thin film transistor is composed of a semiconductor layer which forms a channel with a gate electrode, and a source electrode and a drain electrode which are a part of the data line. In the manufacture of thin film transistors, first, a metal layer is laminated with a wiring material for a gate or source / drain electrode on a substrate, followed by an etching process in which the metal layer is etched with a corrosive gas or solution to realize a desired electric circuit line.

If the etchant is repeatedly etched using the same etchant, the concentration of metal ions in the etchant will increase, and if the metal ion concentration is above a certain level, the hydrolytic etchant containing hydrogen peroxide (H ₂ O ₂ ) and

There is a problem in that process margin and storage stability are low, and there is a risk of explosion due to a chemical reaction between metal ions and hydrogen peroxide.

In the case of non-aqueous etching solutions that do not contain hydrogen peroxide, if the concentration of metal ions exceeds the critical point, the properties as an etchant are lost and the number of cumulative treatments is small, storage at room temperature is difficult, and etching solutions having different compositions depending on the thickness of the metal film There is a problem. In addition, when the thin film to be etched includes copper (Cu), there is a problem that the non-aqueous etching solution reacts with copper ions and chloride ions to generate precipitates.

Accordingly, it is an object of the present invention to provide a composition that greatly improves aging properties, has a higher etching rate for metals, and does not cause poor storage stability and precipitation, which is a problem of conventional etching solutions, compared with etching solutions that do not use hydrogen peroxide . It is another object of the present invention to provide a metal wiring forming method for etching a metal film in a predetermined pattern in a process of manufacturing a metal wiring using the etching composition.

In order to attain the above object, the present invention provides a process for producing a nitrogen-containing heterocyclic compound, which comprises a persulfate, a fluorine-containing compound, a 4 nitrogen ring compound, a 2 chlorine compound and water, 2 < / RTI >

The present invention also provides a method of manufacturing a semiconductor device, comprising: forming a metal film containing copper on a substrate; And an etching step of etching the metal film in a predetermined pattern using the etching solution composition.

The etchant composition according to the present invention has higher storage stability, no precipitate, higher etching rate against metal, and improved aging properties than conventional non-aqueous etching solutions.

1 is a scanning electron micrograph of a sample comprising a laminated titanium / copper double film and a photoresist pattern etched with the etching compositions of Examples 1 to 7 of the present invention.
2 is a scanning electron micrograph of a sample comprising a laminated titanium / copper double film and a photoresist pattern etched with the etching compositions of Comparative Examples 1 to 9 of the present invention.

Hereinafter, the present invention will be described in more detail with reference to the accompanying drawings.

The etchant composition according to the present invention is characterized in that the etchant composition comprises persulfate, a fluorine-containing compound, a 4 nitrogen-containing cyclic compound, a 2 chlorine compound and water, wherein the content ratio of the 4 nitrogen-containing cyclic compound to the 2 chlorine compound is 1: 1.4 to 1: Lt; / RTI >

The persulfate of the etchant composition is decomposed into a self-decomposition reaction during the copper etching process as an etchant for etching the copper film, so that the etching rate of the copper film may be lowered. The content of the persulfate may be 0.1 to 25% by weight, preferably 0.5 to 20% by weight, more preferably 1 to 18% by weight, and most preferably 5 to 15% by weight. If the persulfate content is higher than 25 wt%, the etch rate is too high to control the etching degree, so that the metal film containing copper can be over-etched. If the persulfate content is lower than 0.1 wt%, the etching rate may decrease, and sufficient etching may not be performed. Specific examples of the persulfate include ammonium persulfate ((NH ₄ ) ₂ S ₂ O ₈ ), sodium persulfate (Na ₂ S ₂ O ₈ ) and potassium persulfate (K ₂ S ₂ O ₈ ) Or a mixture of two or more thereof.

The fluorine-containing compound of the etching solution composition may be a titanium etchant, and the content of the fluorine-containing compound may be 0.01 to 3% by weight, preferably 0.01 to 1% by weight, and most preferably 0.05 to 0.7% by weight. When the content of the fluorine-containing compound is higher than 3% by weight, occurrence of undercut due to the titanium overgrowth increases, and not only the titanium but also the glass substrate on which the titanium is laminated can be over- Is difficult to etch. Specific examples of the fluorine-containing compound include hydrofluoric acid (HF), ammonium fluoride (NH4F), potassium fluoride (KF), sodium fluoride (NaF), ammonium fluoride (F2H5N), potassium hydroxide (KHF2) ), And they may be used alone or in combination of two or more.

), 아미노테트라졸포타슘염(aminotetrazole of potassium salt), 메틸테트라졸(methyltetrazole,

)등이 있으며, 단독 또는 2종이상 혼합하여 사용할 수 있다.The content of the 4 nitrogen-containing cyclic compound is 0.01 to 2% by weight, preferably 0.05 to 1.5% by weight, and most preferably 0.1 to 1% by weight. The 4 nitrogen-containing cyclic compound of the etching composition is a corrosion inhibitor of copper. . When the nitrogen-containing cyclic compound is more than 2% by weight, the etching rate of the etchant composition is too slow by the 4-nitrogen cyclic compound to deteriorate the processability. If the nitrogen-cyclic compound is less than 0.01% by weight, It is difficult to do. Specific examples of the nitrogen-4 cyclic compound include aminotetrazole,

), Aminotetrazole of potassium salt, methyltetrazole,

), And they may be used alone or in combination of two or more.

The dichoric compound of the etchant composition is a taper angle increasing and erosion inhibitor, and the content of the ditallow compound may be 0.05 to 8 wt%, preferably 0.1 to 5 wt%, and most preferably 0.3 to 3 wt% . If the amount of the chlorine compound is higher than 8 wt%, an excessive angle may occur and the metal wiring may be lost. If the chlorine compound is less than 0.05 wt%, the etching rate of the metal film containing copper may be lowered and the etching profile may become poor. Specific examples of the chlorine compound include magnesium chloride (MgCl 2), calcium chloride (CaCl 2), and copper chloride (CuCl 2). These chlorine compounds may be used singly or in combination of two or more.

The etchant composition may further comprise a hydrogen sulphate salt. The hydrogen peroxide of the etchant composition is a persulfate stabilizer. When a metal film containing copper is etched using a persulfate-based compound, the etching performance is impaired due to the decomposition of the sulfate compound and the sulfate compound. The rate of decomposition of the sulfate is delayed to keep the etching rate of the copper-containing metal film constant. The content of the hydrogen sulphate salt may be 0.05 to 8% by weight, preferably 0.1 to 5% by weight, and most preferably 0.5 to 3% by weight. If the amount of the hydrogen peroxide is more than 8 wt%, the etching rate of the copper film is too fast to cause erosion failure. If the amount is less than 0.05 wt%, the persulfate-based compound has no decomposition inhibiting effect and storage stability may be impaired. Specific examples of the hydrogen sulphite salt include ammonium hydrogen sulfate (NH ₄ HSO ₄ ), lithium hydrogen sulfate (LiHSO ₄ ), potassium hydrogen sulfate (KHSO ₄ ), sodium hydrogen sulfate (NaHSO ₄ ) Can be mixed and used.

The etchant composition may further comprise a sulfonic acid compound. The sulfonic acid compound of the etchant composition is used as a co-oxidant and serves as a buffer to supplement the oxidative power consumed by the reaction with the copper compound and to maintain the etching rate. The content of the sulfonic acid compound may be 0.1 to 10% by weight, preferably 0.5 to 7% by weight, and most preferably 1 to 5% by weight. If the concentration of the sulfonic acid compound is higher than 10 wt%, the etching rate will increase with the contamination concentration of Cu, and if it is lower than 0.1 wt%, the etching rate will decrease due to the contamination with Cu, and the performance may be deteriorated. Specific examples of the sulfonic acid compound include sulfamic acid (H ₃ NSO ₃ ), ammonium sulfonic acid, cyclic sulfonic acid compound, and hydrocarbon sulfonic acid compound. These sulfonic acid compounds may be used singly or in combination of two or more. .

), 부탄 술톤(butane sultone,

), 프로펜 술톤(propene sultone,

) 등을 들 수 있으며, 단독 또는 2종이상 혼합하여 사용할 수 있다. 상기 탄화수소계 술폰산 화합물은 탄소수 1 내지 20, 바람직하게는 탄소수 2 내지 10, 더욱 바람직하게는 탄소수 3 내지 6의 탄화수소계 술폰산 화합물로, 구체적인 예로는 메탄술폰산(methane sulfonic acid, CH₃SO₃H), 에탄술폰산(ethane sulfonic acid, CH₃CH₂SO₃H), 벤젠술폰산(benzene sulfonic acid, C₆H₆SO₃H), 톨루엔술폰산(toluene sulfonic acid, 예를 들어 p-CH₃C₆HSO₃H) 등을 들 수 있으며, 단독 또는 2종이상 혼합하여 사용할 수 있다.The cyclic sulfonic acid compound is a cyclic sulfonic acid compound having 1 to 20 carbon atoms, preferably 2 to 10 carbon atoms, and more preferably 3 to 6 carbon atoms. Specific examples thereof include propane sultone,

), Butane sultone

), Propene sultone,

), And they may be used alone or in combination of two or more. The hydrocarbon-based sulfonic acid compound is a hydrocarbon-based sulfonic acid compound having 1 to 20 carbon atoms, preferably 2 to 10 carbon atoms, and more preferably 3 to 6 carbon atoms. Specific examples thereof include methane sulfonic acid (CH ₃ SO ₃ H) , Ethane sulfonic acid (CH ₃ CH ₂ SO ₃ H), benzene sulfonic acid (C ₆ H ₆ SO ₃ H), toluene sulfonic acid (for example, p-CH ₃ C ₆ HSO ₃ H). These may be used singly or in combination of two or more.

The etchant composition may further comprise a sulfating agent and / or a sulfating agent salt. Antioxidants and / or antioxidant salts of the etching liquid compositions and corrosion inhibition and 4 nitrogen serving to adjust the second chlorine compound and a metal film etching rate to the taper angle regulating role cyclic compounds and two chlorine compound and a Cu ^{2 +} Generation of the poorly soluble precipitate generated by the reaction between the ions can be suppressed. The content of the antioxidant and / or its salt may be 0.001 to 10% by weight, preferably 0.005 to 7% by weight, and most preferably 0.01 to 5% by weight of the total composition. If the antioxidant and / or the salt thereof is more than 10% by weight, the etching ability of copper may be decreased and the etching time may be prolonged in the process, so that productivity may be problematic. When the amount is less than 0.001% by weight, can do. Specific examples of the antioxidant include ascorbic acid, glutathione, lipoic acid, and uric acid, and they may be used alone or in combination of two or more. The salt of the antioxidant of the etchant composition may be a salt of the compound of the antioxidant, and specific examples thereof may be at least one selected from the potassium salt, the sodium salt and the ammonium salt of the compound selected from the specific examples of the antioxidant.

In the present invention, the weight of other components other than water in the total etching solution, such that the sum of the weight percentages of the remaining components other than water in the total etchant composition and the weight percentage of water is 100 wt% % Of the total. As the water used for the etchant, it is preferable to use water or ultrapure water of semiconductor grade.

If necessary, the inorganic acid which can be further included in the etchant composition may be used as an acidity controlling agent capable of controlling the acidity of the etchant composition, and the content of the inorganic acid may be 0.1 to 0.9% by weight, preferably 0.1 to 0.7% , And most preferably 0.3 to 0.5 wt%. If the inorganic acid content is higher than 0.9% by weight, the acidity of the etchant composition becomes high and the role of the antioxidant can not be controlled. If it is lower than 0.1% by weight, the acidity may be low and precipitation may occur. Specific examples of the inorganic acid include nitric acid (HNO ₃ ), sulfuric acid (H ₂ SO ₄ ) and the like, either singly or in combination.

The acid value of the etchant composition may be 2 to 6, preferably 2 to 5.5, more preferably 3 to 5. If the acid value of the etchant composition is less than 2, the copper ion reducing ability of the antioxidant may increase and the etching stability may deteriorate. If the acid value of the etchant composition exceeds 6, the oxidant content increases, Can occur. The acidity refers to the ability of the base to neutralize the hydrogen ions, and the hydrogen ion from the acid neutralizes the base. The higher the acidity (i.e., the higher the acidity value), the stronger the oxidizing power.

In addition, the 4 nitrogen-containing cyclic compound and the 2 chlorine compound in the etching liquid composition are the main compounds for generating a poorly soluble precipitate. When the acid value of the etchant composition is 2 to 6, the weight ratio of the 4 nitrogen- Range is from 1: 1.4 to 1: 2, preferably from 1: 1.4 to 1: 1.8, and most preferably from 1: 1.4 to 1: 1.6. Even if there is an antioxidant, a poorly soluble precipitate is generated if the ratio and acidity of the 4 nitrogen-containing cyclic compound and the ditrogen compound are out of the above range.

The etching solution composition of the present invention can be used as an etching solution for a metal wiring which can be used for a thin film transistor liquid crystal display device or the like. The metal wiring may be formed by etching and patterning a metal film. The metal film may be one of a titanium film or a titanium alloy film as a copper film, a copper alloy film, and a copper lower film. The method for forming a metal wiring according to the present invention includes the steps of forming a multi-film including at least one of a titanium film (Ti) and a copper film as a single film or a lower film including copper on a substrate; And etching the single layer or the multi layer with an etchant. The etchant may include persulfate, hydrogen sulfide, fluoride, 4-nitrogen cyclic compound, antioxidant, dicarbon compound, and sulfonic acid compound, and may further include inorganic acid if necessary. 1: 1.4 to 1: 2, and the overall acidity of the composition is 2 to 6. The multilayer includes a top film including a titanium film or a titanium alloy film and a top film including copper, and etching the multi-film with an etchant may collectively etch the top film and the bottom film.

The etchant composition according to the present invention suppresses generation of poorly soluble precipitates due to the reaction of copper divalent ions (Cu ^{2 +} ), 4 nitrogen cyclic compounds and chloride ions generated during the etching process of copper and / or copper alloy, It is possible to control the erosion due to precipitates and the defective short circuit process, and the storage stability is improved by the hydrogen sulphate, and as the stability is increased, the cumulative number of sheets can be increased and the process cost can be lowered. Also, by using sulfonic acid compound as a co-oxidant, it has a buffering effect that maintains the etching rate because it serves to supplement oxidizing power which is decreased when the etching solution is continuously used.

The poorly soluble precipitate is formed as a complex between the 4-nitrogen cyclic compound and the Cl ^- ion of the Cu ^{2 +} ion and the chlorine compound occurring during the copper film etching process. The antioxidant or antioxidant salts of the etchant composition of the present invention reduce the Cu ^{2 +} ion to Cu ^{1 +} ions and generate a chemical bond between the poorly soluble Cu ^{2 +} ion and the Cl ^- ion and the 4-nitrogen cyclic compound And has a great effect on inhibiting precipitates.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited by the following Examples.

[Examples 1 to 9 and Comparative Examples 1 to 9] etchant composition

The etching solutions of Examples 1 to 9 and Comparative Examples 1 to 9 according to the etching solution composition of the present invention were prepared as shown in Table 1 below. The percentages in Table 1 below are% by weight.

Sulfuric acid
salt
(%) Sulfuric acid
Hydrogen
salt
(%) nitric acid
(%) Partial payment
ammonium
(%) Amino
Tetrazole
(%) Ascorbic acid
(%) Chloride
Magnesium (%) methane
Sulfonic acid
(%) Sulpa
Mixan
(%) Acidity
(Acidity) Example 1 12 0.5 0 0.5 0.5 One 0.7 2 2 4.5 Example 2 10 One 0.5 0.5 0.6 One 0.9 One 1.5 6 Example 3 8 2 0 0.5 0.8 2 1.6 4 2 5.8 Example 4 12 0.5 0.5 0.5 0.6 One 1.2 One 3 5 Example 5 10 One 0.5 0.5 0.6 One 1.2 One One 2 Example 6 8 2 0 0.5 0.4 0.3 0.6 2 One 3.5 Example 7 8 3 0 0.4 One 4 1.5 One One 3.2 Example 8 15 5 0.9 One 1.5 One 2.2 0 0 6 Example 9 12 0 0 0.5 0.5 One 0.7 One 2 4.5 Comparative Example 1 8 0.5 0 0.5 0.4 One 1.2 One One 3 Comparative Example 2 10 0.5 0 0.4 One One One 2 2 4.5 Comparative Example 3 26 2 0.5 0.5 0.4 0.3 0.6 0.5 0.5 4.8 Comparative Example 4 10 One 0.5 0.5 0.6 One 1.2 0.05 0 1.9 Comparative Example 5 10 One 0.5 0.005 0.6 One 0.9 One 1.5 6 Comparative Example 6 10 One 0.5 0.5 0.6 0 0.7 One 3 5.8 Comparative Example 7 10 One One 0.5 0.6 One 0.9 One 1.5 6.4 Comparative Example 8 0 2 0.5 0.5 0.4 0.3 0.6 0.5 0.5 1.6 Comparative Example 9 10 One 0.5 4 0.6 One 0.9 One 1.5 3.6

[Experimental Example 1] Etching fluid angular velocity , CD Skew ( one side ), taper angle measurement

Etch rate (E / R), CD skew (E / R), and the like were measured for each sample by the etching compositions of Examples 1 to 9 and Comparative Examples 1 to 9, respectively, on a sample containing a laminated titanium / And the taper angle were measured using a scanning electron microscope (SEM). The results are shown in Table 2 below. In FIGS. 1 and 2, scanning electron micrographs of Examples and Comparative Examples are shown .

The copper etching rate (Cu E / R) is an appropriate etch rate in the range of 200 Å / sec to 300 Å / sec. CD skew (Cut dimension skew) (unidirectional) indicates the distance between the photoresist tip and the copper tip. This distance should be in the appropriate range for tapered etching without step differences. The appropriate range of the CD skew (one side) is 0.6 탆 to 0.8 탆. The taper angle means an inclination viewed from the side of the etched metal film, and an appropriate value is 60 to 70 degrees.

Etch characteristics Precipitate Cu E / R
(Å / sec) CD-Skew (one side, ㎛) Taper angle
(°) Precipitate Example 1 232 0.6 60 No precipitation Example 2 235 0.73 63 No precipitation Example 3 230 0.61 62 No precipitation Example 4 250 0.72 65 No precipitation Example 5 245 0.66 60 No precipitation Example 6 235 0.68 62 No precipitation Example 7 240 0.66 65 No precipitation Example 8 255 0.21 60 No precipitation Example 9 185 0.62 65 No precipitation Comparative Example 1 139 0.26 60 Precipitation occurrence Comparative Example 2 120 0.28 57 Precipitation occurrence Comparative Example 3 298 1.04 88 No precipitation Comparative Example 4 125 0.5 57 Precipitation occurrence Comparative Example 5 248 0.5 35 No precipitation Comparative Example 6 150 0.16 62 Precipitation occurrence Comparative Example 7 240 0.95 72 Precipitation occurrence Comparative Example 8 10 0.33 43 Precipitation occurrence Comparative Example 9 140 0.46 79 No precipitation

Referring to Table 2, in the case of Comparative Examples 1, 2, 4, 6, and 8, two or more of the etching rate, CD skew, and taper angle do not satisfy the above-described appropriate ranges . In Comparative Examples 3, 5, and 9, poorly soluble precipitates did not occur, but it was confirmed that two or more of the etching rate, CD skew, and taper did not satisfy the appropriate range described above.

In Examples 1 to 7, the etching rate, the CD skew, and the taper angle all met the appropriate ranges described above without causing poor solubility precipitation.

In Examples 8 and 9, CD skew and etch rate were not satisfied, respectively, but all of the remaining items were satisfied.

As a result of the above experiment, when the ratio of the 4 nitrogen-containing cyclic compound to the 2-chlorine compound did not satisfy 1: 1.4 to 1: 2, the acidity was out of 2 to 6 and the case where the antioxidant was removed, It was confirmed that a poorly soluble precipitate was generated as shown in FIG.

[Experimental Example 2] Measurement of storage stability of an etchant composition

Experimental Example 2-A: Evaluation of Precipitation

5 kg of the etching compositions of Example 1 and Comparative Example 6 of the present invention were prepared and stored for a predetermined period at a low temperature to compare the amounts of precipitates generated.

2 days 4 days 6 days 8 days 10 days Example 1 0g 0g 0g 0g 0g Comparative Example 6 0.1220 g 0.8325 g 1.7154 g 2.5012 g 3.8147 g

Referring to Table 3, it can be confirmed that the poorly soluble precipitate does not occur even when the storage period is increased in the case of Example 1. From these results, it was confirmed that when an antioxidant is contained, the generation of precipitates can be suppressed when stored for a long period of time.

Experimental Example 2-B: Storage stability evaluation

Reference etching was performed using the etching solutions of Examples 1 and 9 of the present invention and the etching compositions of Examples 1 and 9 were stored at a temperature of about 10 캜 for a predetermined period of time. The etch test was conducted again under the same conditions every day and compared with the reference test results, and the results are summarized in Tables 4 and 5 below.

Example 1 Ref 1 day 2 days 3 days Cu EPD ◎ ◎ ◎ ○ CD-Skew (one side) ◎ ◎ ◎ ○ Taper angle ◎ ◎ ◎ ○

Example 9 Ref 1 day 2 days 3 days Cu EPD ◎ ○ △ △ CD-Skew (one side) ◎ ○ △ △ Taper angle ◎ ○ △ △

◎: Excellent (less than 5% change from reference)

○: Excellent (within 10% of reference variation)

△: Normal (change over 10% compared to reference)

Referring to Table 4, it can be seen that the storage stability of Example 1 including the hydrogen sulfate is better than that of Example 9 which does not contain hydrogen sulfate. It can be seen that even when the storage period of the etching composition is increased, the change of the etching rate, the CD skew and the taper angle is not large and the storage stability is excellent.

[Experimental Example 3] Evaluation of Reliability According to Increase in Number of Etchant Treatment

The copper ion concentration was increased with respect to the etching solution according to Example 1 of the present invention, and the evaluation of the number of treated substrates was carried out as follows.

Reference etch was performed using the etchant of Example 1, etching test was performed by adding copper powder at 1,000 ppm, and the results were compared with reference test results. The results are summarized in Table 6 below.

Ref 1000ppm 2000 ppm 3000ppm 4000ppm Cu EPD ◎ ◎ ◎ ◎ ◎ CD-Skew (one side) ◎ ◎ ◎ ◎ ◎ Taper angle ◎ ◎ ◎ ◎ ◎

◎: Excellent (less than 10% variation relative to reference)

Poor: Poor (10% variation compared to reference)

Referring to Table 6, it can be seen that the etching rate, the CD skew, and the taper angle are not significantly changed even when the copper ion concentration in the etching composition 1 is increased. Therefore, it can be seen that the etching composition has reliability

Claims (15)

A nitrogen-containing compound, a persulfate, a fluorine-containing compound, a 4-nitrogen ring compound, a 2-chlorine compound and water, wherein the content ratio of the 4-nitrogen ring compound and the ditallow compound is 1: 1.4 to 1: 2. The etchant composition of claim 1, wherein the acidity is from 2 to 6. The etchant composition of claim 1, further comprising a hydrogen sulphate. The etchant composition of claim 1, further comprising a sulfonic acid compound. The etchant composition of claim 1, further comprising a sulfurating agent or a salt thereof. The etchant composition of claim 1, further comprising an inorganic acid. The composition according to claim 1, wherein the persulfate is present in an amount of 0.1 to 25% by weight, the fluorine-containing compound is 0.01 to 3% by weight, the 4-nitrogen ring compound is 0.01 to 2% By weight based on the total weight of the composition. The etchant composition of claim 7, further comprising 0.05 to 8 wt% of a sulfuric acid salt, 0.1 to 10 wt% of a sulfonic acid compound, 0.001 to 10 wt% of an antioxidant or salt thereof, and 0.1 to 0.9 wt% of inorganic acid. The etchant composition of claim 8, wherein the acidity is from 2 to 6. 5. The method according to claim 4, wherein the sulfonic acid compound is selected from the group consisting of sulfamic acid (H3NSO3), ammonium sulfonic acid, cyclic sulfonic acid compound having 1 to 20 carbon atoms and hydrocarbon sulfonic acid compound having 1 to 20 carbon atoms At least one selected. The etchant composition according to claim 1, wherein the 4-nitrogen cyclic compound is at least one selected from the group consisting of aminotetrazole, aminotetrazole of potassium salt and methyltetrazole. The antioxidant or salt thereof according to claim 5, wherein the antioxidant or salt thereof is at least one kind of antioxidant selected from the group consisting of ascorbic acid, glutathione, lipoic acid and uric acid, An antioxidant, and a salt selected from the group consisting of a potassium salt, a sodium salt, and an ammonium salt of a compound selected from the group consisting of an antioxidant, an antioxidant, and an antioxidant. The etchant composition according to claim 1, wherein the chlorine compound is at least one selected from the group consisting of magnesium chloride (MgCl ₂ ), calcium chloride (CaCl ₂ ), and copper chloride (CuCl ₂ ). 7. The etchant composition according to claim 6, wherein the inorganic acid is at least one selected from the group consisting of nitric acid (HNO3) and / or sulfuric acid (H2SO4). 4. The etchant composition according to claim 3, wherein the hydrogen sulfide is at least one selected from the group consisting of ammonium hydrogen sulfate (NH4HSO4), lithium hydrogen sulfate (LiHSO4), potassium hydrogen sulfate (KHSO4) and sodium hydrogen sulfate (NaHSO4).

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