KR20190111658A - ITO / Ag multi-layer etchant composition containing no phosphate - Google Patents

Abstract

The present invention relates to an ITO/Ag multi-layer etchant composition without phosphate used in a metal wire manufacturing process in manufacturing a display and to a metal wiring forming method using the same. The etchant composition comprises: anion of an organic acid compound; anion of a sulfonic acid compound; nitrate ions; sulfate ions; a dicarbonyl compound including nitrogen; and remaining water, wherein the anion content of the organic acid compound is 35 to 50 wt%.

Description

ITO / Ag multi-layer etchant composition containing no phosphate

The present invention relates to an ITO / Ag multi-film etchant composition containing no phosphate, and more particularly, to an ITO / Ag multi-film etchant composition containing no phosphate used in the metallization manufacturing process in the display manufacturing.

Currently, the trend of the display market shows the limitations of LCD, and due to the advantages of OLED, development and application of various ranges are being attempted in OLED.

OLEDs are display devices with many advantages. Compared to LCD, OLED can make the contrast ratio, reagent angle, response speed and thickness of display device thin, and can be applied to flexible display because of its wide viewing angle and shape deformation.

In addition, OLEDs do not use BLU (Back light unit) and color filter structurally. This is because OLEDs do not need a device that generates other constant light as a self-luminous device. Therefore, in OLED, specific wiring is made by using ITO / Ag / ITO multilayer including Ag to prevent light loss. ITO stands for Idium Tin Oxide and is a transparent and electrically conductive material. ITO is used in various display panels, electromagnetic wave shielding films, organic ELs, etc. because it exhibits excellent electrical conductivity and high transmittance in the visible region with a bandgap of 2.5 eV or more. In addition, it has excellent electrode pattern processability, excellent chemical and thermal stability, and low resistance during coating, compared to other transparent electrode materials. Ag has low resistivity, high brightness, and high conductivity, which is advantageous in constructing the OLED wiring.

However, when ITO / Ag / ITO thin film containing Ag is used, the CD-Skew of ITO / Ag / ITO is largely formed during the wiring etching process using the existing etching liquid composition, and the margin for wiring width is bad. Wiring uniformity was not good due to the formation of non-uniform CD-Skew according to the etching process environment. In addition, Ag residue may occur due to non-uniform etching, and reducing Ag precipitates may be generated by reacting with the metal constituting the lower wiring. Ag residues and precipitates have a problem of generating defects called dark spots. In particular, in the lower wiring that causes Ag-reducing precipitates, Ti / Al / Ti wiring containing Al is mainly used, and when Al etching occurs because the etching process is performed using an existing etchant composition, Al damage occurs. The generated electrons react with Ag ions to cause Ag reducing precipitates, and the Al has damage, but Ti does not have damage, so that the Ti tip protrudes like a tip, after the etching process. It breaks and moves to the main wiring part, causing dark spots and wiring defects. This is due to a specific composition, and the development of a new etchant that does not contain a specific composition is required.

Accordingly, it is an object of the present invention to provide a composition which does not contain phosphate and improves small lateral side (CD-Skew) and time-lapse even when collectively etching ITO / Ag / ITO wiring.

Another object of the present invention is to provide a composition which does not have a problem for silver (Ag) residue due to high etching rate for silver (Ag), and does not cause Al damage so that precipitation and Ti tip do not occur.

In order to achieve the above object, the present invention includes an anion of an organic acid compound, an anion of a sulfonic acid compound, a nitrate ion, a sulfate ion, a dicarbonyl compound including nitrogen and a residual amount of water, It provides an etching liquid composition is content of 35 to 50% by weight.

Here, the anion of the organic acid compound is acetate (acetate), maleate (malate), citrate (citrate), tartarate (Tartarate), lactate (Lactate), Formate (Succinate), It is preferably selected from the group consisting of fumarate.

The ITO / Ag multi-layered etching liquid composition which does not include the phosphate according to the present invention has a high etching rate with respect to silver (Ag) and does not include phosphate, and can produce an etching liquid composition with improved small unilateral (CD-Skew) and aging. Can be.

1 is a Scope and SEM picture of a sample comprising a laminated ITO / Ag / ITO multilayer and a photoresist pattern etched with the etching composition of Examples 1 to 15 of the present invention.
FIG. 2 is a Scope and SEM image of a sample including a laminated ITO / Ag / ITO multilayer and a photoresist pattern etched with the etching compositions of Comparative Examples 1 to 23 of the present invention. FIG.

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

The etchant composition according to the present invention comprises an anion of an organic acid compound, an anion of a sulfonic acid compound, a nitrate ion, a sulfate ion, a dicarbonyl compound including nitrogen and a residual amount of water, wherein the anion of the organic acid compound is 35 to 50% by weight of an etchant composition is provided.

The nitrate ion of the etchant composition is a main oxidizing agent which oxidizes the Ag film mainly, and the nitrate ion (4NO ₃ ⁻ ) reacts with silver (Ag) during the Ag etching process to etch the Ag film. In this reaction, the inorganic acid compound nitric acid (HNO ₃ ) is decomposed into silver nitrate (AgNO ₃ , Silver Nitrate), nitrogen monoxide (NO, Nitric oxide) and water (Water, H ₂ O) to reduce the etching rate of the Ag film. . The nitrate content may be 1 to 20% by weight, preferably 5 to 15% by weight. If the nitrate ion is higher than 20% by weight, the etching rate is too high to control the etching degree, thereby over-etching the metal film containing Ag. If the nitrate ion is lower than 1% by weight, the etching rate may be reduced and not sufficient etching.

The anion of the organic acid compound in the etchant composition is an auxiliary oxidant for nitrate ions which are silver (Ag) main oxidizing agents. When nitrate ions (4NO ₃ −) react with Ag to etch Ag, nitrate ions are decomposed into 3AgNO ₃ ⁻ , NO and H ₂ O, and the etching rate may be lowered. The anion of the organic acid compound may decompose nitrate ions. By inhibiting the etching rate of the silver (Ag) -containing metal film is kept constant. In addition, the anion of the organic acid compound may include a form of an anion salt in which hydrogen ions are separated from the organic acid compound.

The content of the anion of the organic acid compound may be 35 to 50% by weight, preferably 40 to 48% by weight. If the anion of the organic acid compound is higher than 50% by weight, the etching rate of the silver (Ag) film is too fast to cause erosion defects. If the anion of the organic acid compound is lower than 35% by weight, the nitrate ion may decrease the decomposition inhibitory effect, thereby inhibiting stability. Ag residue may occur.

Specific examples of the anion of the organic acid compound is acetate ^{_{(acetate, CH 3 COO -)}} , maleate (malate), citrate (citrate), tartrate (Tartarate), lactate (Lactate), formate (Formate), It may be at least one selected from Succinate, Fumarate, and mixtures thereof. The organic acid compound can be used by selecting both anhydrous and hydrous.

In an embodiment according to the present invention, the anion of the organic acid compound is an anion and citrate of at least one first organic acid compound selected from acetate, lactate, formate, and mixtures thereof. And an anion of at least one second organic acid compound selected from the group consisting of malate, tartarate, succinate, fumarate, and mixtures thereof. In another embodiment, the anion of the first organic acid compound may include acetate, and the anion of the second organic acid compound may include citrate. With respect to 100% by weight of the etchant composition, acetate ) May be included in the content of 15 to 25% by weight, citrate (citrate) may include 20 to 25% by weight.

Anion of the sulfonic acid compound of the etching liquid composition as a secondary oxidizing agent, nitric acid ion (4NO3 ^-) is the (3Ag) reacts with the case of etching a film Ag, a nitrate ion 3AgNO ₃ - are broken down into the NO and H ₂ O etching rate The anion of the sulfonic acid compound slows the rate of decomposition into nitrate ions, thereby maintaining a constant etching rate of the Ag-containing metal film. In addition, the anion of the sulfonic acid compound may include a form of an anion salt in which hydrogen ions are separated from the sulfonic acid compound.

The anion content of the sulfonic acid compound may be 1 to 10% by weight, preferably 2 to 8% by weight. If the anionic salt of the sulfonic acid compound is higher than 10% by weight, the etch rate of the Ag film may be excessively high, which may cause erosion defects. If the anion salt of the sulfonic acid compound is higher than 1% by weight, the nitrate may have a degradation inhibitory effect, thereby reducing stability, and residues may be inhibited. May occur.

The anion salt of the sulfonic acid compound is methanesulfonate, p-toluenesulfonate, benzosulfonate, aminomethylsulfonate, amino methylsulfonate, sulfamate and mixtures thereof It may be at least one selected from. The anion of the sulfonic acid compound is hydrogen ion in methanesulfonic acid, p-toluenesulfonic acid, benzenesulfonic acid, benzenesulfonic acid, amino methylsulfonic acid, sulfamic acid. It may be in the form of a fallen anionic salt.

Sulfate ions of the etchant composition is a stock etchant for etching indium-tin oxide (hereinafter, ITO) mainly, and in the absence of sulfate ions, ITO is not etched. The amount of sulfate ion may be 10 to 20% by weight, most preferably 12 to 19% by weight. If the sulfate ion is higher than 20% by weight, the etching rate of the ITO film is too fast to cause erosion defects. If the sulfate ion is lower than 10% by weight, the etching rate of ITO decreases, and ITO and Ag residues may occur. In addition, the sulfate ion may include the form of a salt in which the hydrogen ion is separated from the sulfate compound, and is an anion of the sulfate compound, for example, sulfate.

The sulfate ion is sulfuric acid (H ₂ SO ₄ ), ammonium hydrogen sulfate (NH ₄ ) HSO ₄ ), potassium hydrogen sulfate (KHSO ₄ ), sodium hydrogen sulfate (Sodium hydrogen sulfate , NaHSO ₄ ), Ammonium sulfate (NH ₄ ) ₂ SO ₄ ), Potassium sulfate (K ₂ SO ₄ ), Sodium sulfate (Na ₂ SO ₄ ) and mixtures thereof It may be in the form of a fallen anion. The sulfuric acid compound can be used both anhydrous and hydrous.

Dicarbonyl (Dicarbonyl) compound containing nitrogen of the etchant composition as an etch regulator for ITO, Ag, Al, prevents excessive CD-Skew formation during the formation of wiring, prevents damage to Al and precipitates Ag and Ti Tip It suppresses the occurrence and prevents CD-Skew change from occurring with the Ag concentration. Specifically, when a certain amount of a dicarbonyl compound including nitrogen in the etchant composition is used, as an etching regulator for ITO, Ag, and Al, the nitrogen having the dicarbonyl compound on the surface of the metal oxidized by the oxidant and Oxygen is adsorbed effectively, it controls the etching by preventing excessive etching, it can form Low CD-Skew, prevents Ag damage by preventing Al damage, and controls the CD-Skew change according to the increase of Ag concentration. It has the effect of greatly improving the cumulative buying performance.

In the case of the dicarbonyl compound derivative containing nitrogen, two or more derivatives must be mixed and used. Specific examples of the dicarbonyl compound containing nitrogen include asparagine (Asparagine, C ₄ H ₈ N ₂ O ₃ ), iminodiacetic acid (C ₄ H ₇ NO ₄ ), and imidazolidine-2. Imidazolidine-2,4-dione, C ₃ H ₄ N ₂ O ₂ , Succinimide, C ₄ H ₅ NO ₂ , Glutarimide, C ₅ H ₇ NO ₂ ), Glutamic acid (C ₅ H ₉ NO ₄ ), Aspartic acid (C ₄ H ₇ NO ₄ ), Pyro-glutamic acid (C ₅ H ₇ NO ₃ ), Hippuric acid ( Hippuric acid, C ₉ H ₉ NO ₃ ) and mixtures thereof. Dicarbonyl compounds, including nitrogen, can be used for both anhydrous and hydrous.

The total content of the dicarbonyl compound including the nitrogen may be 2 to 10% by weight, most preferably 3 to 8% by weight. When the dicarbonyl compound containing nitrogen is higher than 10% by weight, the ITO and Ag etching rates are excessively lowered so that no CD-Skew is formed, the Ag residue is generated, and the dicarbonyl compound containing nitrogen is present. If it is lower than 2 wt%, one side (CD-Skew), which is the length from the photoresist end to the metal end, is excessively formed, Al damage occurs, Ag precipitation and Ti tip occur, and the chemical liquid Problems can arise over time.

The etchant composition of the present invention may further include a metal ion. The metal ion is a metal oxidant and has an effect of increasing the ITO etching rate together with sulfate ion. The content of the metal ions may be 0.01 to 2% by weight, most preferably 0.01 to 1.5% by weight. If the metal ion is higher than 2% by weight, the ITO etching rate is excessively high, and CD-Skew is excessively formed. If the metal ion is lower than 0.01% by weight, the ITO etching rate is excessively lowered, resulting in ITO residue and Ag residue. Can be. The metal ion may be in the form of a metal salt. The metal ion may be at least one selected from iron ions, copper ions, magnesium ions, and mixtures thereof.

Specific examples of the metal ion compound include ferric nitrate Fe (NO ₃ ) ₃ , copper nitrate (Copper nitrateCu (NO ₃ ) ₂ ), magnesium nitrate (Magnesium nitrate Mg (NO ₃ ) ₂ ), and mixtures thereof. It may be one or more selected. Metal ion compounds can be used both anhydrous and hydrous. When the iron ion and the nitrate ion are 100% by weight, among them, the iron ion is 0.23 to 3.93% by weight, and when the copper ion and the nitrate ion are 100% by weight, the copper ion is 0.34 to 5.76% by weight, and magnesium When the sum of the ions and the nitrate ions is 100% by weight, the magnesium ion may be 0.16 to 2.79% by weight, and the weight ratio of the iron ion and the nitrate ion may be 99: 1.

In the present invention, the water is the weight of the remaining components other than water in the total etchant so that the sum of the weight percent of the other components other than water and the weight percent of water in the total etchant composition is 100% by weight, even if not explicitly mentioned. Occupies all but%. As water used for the etching solution, it is preferable to use water of semiconductor grade or ultrapure water.

In the etchant composition, the inorganic acid compound has a tendency of excessive formation of CD-Skew due to phosphate in the case of a mixed acid etchant using conventional poorly soluble phosphoric acid, and damage to Al forming another wiring due to phosphate. Due to the reduction precipitation of Ag and Ti Tip does not contain phosphate. In addition, Ag etching by phosphate was replaced with anions of organic acid compounds and sulfonic acid compounds, and ITO etching may be collectively implemented by using anions of hydrogen sulfate compounds and ions of metal oxidant compounds.

The etchant composition of the present invention can be used as an etchant for forming metal wirings that can be used in thin film transistor liquid crystal display devices. The metal line may be formed by etching and patterning a metal layer, and the metal layer may be a multilayer formed of ITO, Ag, and ITO / Ag / ITO. In the method for forming a metal wiring according to the present invention, the wiring is collectively formed during the step of forming a multilayer including Ag including at least one of a single film including Ag, a single ITO film, an upper ITO, and a lower ITO on a substrate. Forming a step. The etchant includes an anion of an organic acid compound, an anion of a sulfonic acid compound, a nitrogen ion of an inorganic acid compound, an anion of a sulfuric acid compound, a dicarbonyl compound including nitrogen, and an ion of a metal ion compound. The multi-layer includes an upper layer including ITO, a lower layer and Ag, and the etching of the multi-layer with an etchant is performed without separating the upper layer and the lower layer into an ITO etching process and an Ag wiring etching process. It can be etched in batches and the process can be simplified by reducing process steps.

The etchant composition according to the present invention is an etchant composition from which the phosphate used in the conventional mixed acid etchant was removed to solve the excessively formed CD-Skew and residue and precipitation that occur during the wiring forming etching process. Phosphate was removed, and the phosphate-deficient portion was developed using an organic acid, sulfonic acid, anion of sulfuric acid compound, dicarbonyl compound including nitrogen, and metal ion compound. Elimination of phosphate eliminated Al damage that occurred in other wirings, and also solved existing reduction Ag precipitation and Ti tip generation. Residuals caused by the loss of Ag's etching ability due to phosphoric acid were removed, and the residues were solved by supplementing the etching ability dropped through the anion of the organic acid compound, and the etching of ITO was performed by removing the etching ability dropped through the sulfate and metal ions. Supplemented.

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 15 and Comparative Examples 1 to 23] Etching Liquid Compositions

The etchant of Examples 1 to 15 and Comparative Examples 1 to 23 according to the etchant composition of the present invention was prepared as shown in Table 1 below. % In Table 1 is% by weight.

Citrate
(%) acetate
(%) Methanesulfonate
(%) Nitrate (%) Sulfate
Sulfuric acid
Ions,%) Succinimide (%) Glutamic acid
(Glutamic acid,%) iron
ion
(%) phosphate(%) Example 1 20 15 5 10 15 3 3 0 0 Example 2 20 15 5 10 15 3 3 One 0 Example 3 25 25 5 10 15 3 3 0 0 Example 4 23 20 One 10 15 3 3 0 0 Example 5 23 20 One 10 15 3 3 One 0 Example 6 23 20 10 10 15 3 3 0 0 Example 7 23 20 5 One 15 3 3 0 0 Example 8 23 20 5 One 15 3 3 One 0 Example 9 23 20 5 20 15 3 3 0 0 Example 10 23 20 5 10 10 3 3 0 0 Example 11 23 20 5 10 10 3 3 One 0 Example 12 23 20 5 10 20 3 3 0 0 Example 13 23 20 5 10 15 One One 0 0 Example 14 23 20 5 10 15 5 5 One 0 Example 15 23 20 5 10 15 3 3 0 0 Comparative Example 1 18 13 5 10 15 3 3 0 0 Comparative Example 2 27 27 5 10 15 3 3 0 0 Comparative Example 3 223 20 0.5 10 15 3 3 0 0 Comparative Example 4 23 20 12 10 15 3 3 0 0 Comparative Example 5 23 20 5 0.5 15 3 3 0 0 Comparative Example 6 23 20 5 22 15 3 3 0 0 Comparative Example 7 23 20 5 10 8 3 3 0 0 Comparative Example 8 23 20 5 10 22 3 3 0 0 Comparative Example 9 23 20 5 10 15 3 3 0 One Comparative Example 10 20 15 5 10 15 0 0 0 One Comparative Example 11 23 20 5 10 15 0.5 0.5 0 0 Comparative Example 12 23 20 5 10 15 6 6 0 0 Comparative Example 13 20 15 5 10 15 0 0 0 0 Comparative Example 14 19 14 5 10 15 3 3 0 0 Comparative Example 15 26 26 5 10 15 3 3 0 0 Comparative Example 16 23 20 0.1 10 15 3 3 0 0 Comparative Example 17 23 20 15 10 15 3 3 0 0 Comparative Example 18 23 20 5 0.1 15 3 3 0 0 Comparative Example 19 23 20 5 25 15 3 3 0 0 Comparative Example 20 23 20 5 10 5 3 3 0 0 Comparative Example 21 23 20 5 10 25 3 3 0 0 Comparative Example 22 23 20 5 10 15 0.7 0.8 0 0 Comparative Example 23 23 20 5 10 15 7 8 0 0

Experimental Example 1 Measurement of Etching Speed, CD Skew (One Side), Ag Residue and Precipitation of Etching Solution

Etch rate (E / R), CD for each sample with the etch compositions of Examples 1-15 and Comparative Examples 1-23 on samples comprising stacked ITO / Ag / ITO triple layers and photoresist patterns After measuring the skew (one side), residue and precipitation using Scope and SEM photographs, the results are shown in Table 2 below, and Scope and SEM photographs of Examples and Comparative Examples are shown in FIGS. Indicated. The ITO / Ag / ITO etching rate is a suitable etching rate in the case of 20 kW / sec to 22 kW / sec. CD skew (Cut dimension skew) (one side) indicates the distance between the photoresist end and the ITO / Ag / ITO end. The suitable range of said CD skew (one side) is 0.2 micrometer-0.3 micrometer. Residues and precipitations are marked as 'Yes' if they are present in trace amounts.

Etching characteristics ITO / Ag / ITO E / R
(Å / sec) CD-Skew
(One side, μm) Ag residue Ag precipitation Example 1 20 0.2303 radish radish Example 2 21 0.2496 radish radish Example 3 22 0.2732 radish radish Example 4 20 0.2462 radish radish Example 5 21 0.2574 radish radish Example 6 22 0.2698 radish radish Example 7 20 0.234 radish radish Example 8 21 0.2574 radish radish Example 9 22 0.2768 radish radish Example 10 20 0.2376 radish radish Example 11 21 0.2539 radish radish Example 12 22 0.2811 radish radish Example 13 22 0.2889 radish radish Example 14 21 0.2613 radish radish Example 15 20 0.2415 radish radish Comparative Example 1 15 0.1597 U radish Comparative Example 2 25 0.3513 radish radish Comparative Example 3 18 0.1719 U radish Comparative Example 4 24 0.3356 radish radish Comparative Example 5 16 0.1834 U radish Comparative Example 6 28 0.3428 radish radish Comparative Example 7 16 0.1792 U radish Comparative Example 8 29 0.3437 radish radish Comparative Example 9 24 0.4367 radish U Comparative Example 10 35 0.5116 radish U Comparative Example 11 30 0.4362 radish radish Comparative Example 12 16 0.1873 U radish Comparative Example 13 35 0.5352 radish radish Comparative Example 14 17 0.1988 U radish Comparative Example 15 23 0.3471 radish radish Comparative Example 16 16 0.1872 U radish Comparative Example 17 27 0.3669 radish radish Comparative Example 18 12 0.1251 U radish Comparative Example 19 30 0.4213 radish radish Comparative Example 20 14 0.1483 U radish Comparative Example 21 32 0.4606 radish radish Comparative Example 22 25 0.3471 radish radish Comparative Example 23 12 0.1094 U radish

Experimental results (see Table 2 above), Examples 1 to 15, the precipitation occurrence factor composition is removed from the beginning showing excellent effects in the precipitation experiments. Comparative Example 1 (less than 35% organic acid), Comparative Example 3 (less than 1% anion of sulfonic acid compound) and Comparative Example 5 (less than 1% nitrate ion) have low etching ability on Ag and CD-Skew does not satisfy the range. There was no residue, and Comparative Example 2 (greater than 50% organic acid), Comparative Example 4 (greater than 10% anion of sulfonic acid compound), and Comparative Example 6 (greater than 20% nitrate ion) had excessively improved etching ability on Ag. It can be seen that the CD-Skew is excessively formed. In Comparative Example 7 (less than 10% sulfate ion), the etching ability of ITO was lowered, and residues occurred. In Comparative Example 8 (more than 20% of sulfate ion), the etching ability of ITO was improved, resulting in excessive formation of CD-Skew. Could be confirmed. In the case of containing phosphate as in Comparative Example 9, unlike in Examples 1 to 15 and Comparative Examples 1 to 8, which do not contain phosphate, the etching rate is increased, and accordingly, the CD-Skew is greatly increased to satisfy the CD-Skew. It can exceed the range, and very vulnerable results such as Ag reducing reduction, Al damage generation and Ti Tip generation in the lower wiring can be confirmed.

Experimental Example 2 Precipitation Comparison of Example 15 and Comparative Example 9

Ag precipitation experiments of Example 15 and Comparative Example 9 were carried out in the same manner as in Experimental Example 1. As a result, precipitation of Ag occurred in Comparative Example 9 including ginseng salt, whereas in Example 15 without ginseng salt, it can be seen that the Ag did not occur. Therefore, the present invention can provide an etching solution composition that does not include a phosphate.

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

In the etching solution according to Example 2 of the present invention, the Ag ion concentration was increased to evaluate the number of processed substrates as follows. Reference etching was performed using the etchant of Example 2, Ag powder was added by 500 ppm, and the etching test was performed. The results are summarized in Table 3 below.

Example 2 Ref 500 ppm 1000 ppm 1500 ppm 2000 ppm ITO / Ag / ITO E / R ◎ ◎ ◎ ◎ ◎ CD-Skew (one side) ◎ ◎ ◎ ◎ ◎ Residue ◎ ◎ ◎ ◎ ◎ Precipitation ◎ ◎ ◎ ◎ ◎

◎: Excellent (within 10% of change from reference) / ×: Poor (over 10% of change from reference)

Referring to Table 3, even if the Ag ion concentration increases in the etching composition Example 2, it can be seen that the change in the etching rate, CD skew, residue and precipitation is not large. Therefore, it can be seen that the etching composition has reliability.

Experimental Example 4 Reliability Evaluation of Etching Solution with Time

The time-lapse of the etching solution according to Example 2 of the present invention was increased to evaluate the time-lapse of the substrate as follows. The reference etching was performed using the etchant of Example 2, and the etching test was performed with a time lapse of 12 hours, and the results are summarized in Table 4 below.

Example 2 Ref 12 hours 24 hours 36 hours 48 hours 60 hours 72 hours ITO / Ag / ITO E / R ◎ ◎ ◎ ◎ ◎ ◎ ◎ CD-Skew (one side) ◎ ◎ ◎ ◎ ◎ ◎ ◎ Residue ◎ ◎ ◎ ◎ ◎ ◎ ◎ Precipitation ◎ ◎ ◎ ◎ ◎ ◎ ◎

◎: Excellent (within 10% of change from reference) / ×: Poor (over 10% of change from reference)

Referring to Table 4, even if time elapses in the etching composition Example 2, it can be seen that the change in the etching rate, CD skew, residue and precipitation is not large. Therefore, it can be seen that the etching composition has reliability.

Claims (14)

Anions of organic acid compounds;
Anions of sulfonic acid compounds;
Nitrate ions;
Sulfate ion;
Dicarbonyl compounds including nitrogen; And
Contains residual amount of water,
Etch liquid composition of the anion content of the organic acid compound is 35 to 50% by weight. The method of claim 1, wherein the anion of the organic acid compound is acetate, malate, citrate, tartarate, lactate, formate, succinate. (Succinate), fumarate (fumarate) is selected from the group consisting of, etchant composition. The method of claim 1, wherein the anion of the organic acid compound is an anion and citrate of the first organic acid compound selected from the group consisting of acetate, lactate, formate, and mixtures thereof. Equipped with an anion of a second organic acid compound selected from the group consisting of malate, tartarate, succinate, fumarate and mixtures thereof. The etchant composition of claim 3, wherein the anion of the first organic acid compound is acetate and the anion of the second organic acid compound is citrate. According to claim 4, 100% by weight of the etchant composition, the content of acetate (acetate) is 15 to 25% by weight, the content of citrate (citrate) is an etching solution composition. The method of claim 1, wherein the anion of the sulfonic acid compound is methanesulfonate, p-toluenesulfonate, benzosulfonate, benzenesulfonate, amino methylsulfonate, sulfamate ) And mixtures thereof. According to claim 1, Dicarbonyl containing 1 to 10% by weight of the anion of the sulfonic acid compound, 1 to 20% by weight of nitrate, 10 to 20% by weight of sulfate ion, nitrogen with respect to 100% by weight of the etchant composition The compound comprising 2 to 10% by weight and the balance of water, etching solution composition. The method of claim 1, wherein the sulfate ion is sulfuric acid (Sulfuric acid, H ₂ SO ₄ ), ammonium hydrogen sulfate (NH ₄ ) HSO ₄ ), potassium hydrogen sulfate (KHSO ₄ ), sulfuric acid Sodium hydrogen sulfate (NaHSO ₄ ), Ammonium sulfate (NH ₄ ) ₂ SO ₄ ), Potassium sulfate (K ₂ SO ₄ ), Sodium sulfate (Na ₂ SO ₄ ) and these Etch liquid composition is selected from the anion form in which hydrogen ions are separated from the group consisting of The method of claim 1, wherein the dicarbonyl compound containing nitrogen is asparagine (Asparagine, C ₄ H ₈ N ₂ O ₃ ), iminodiacetic acid (C ₄ H ₇ NO ₄ ), imida Imidazolidine-2,4-dione (C ₃ H ₄ N ₂ O ₂ ), Succinimide (C ₄ H ₅ NO ₂ ), Glutarimide, C ₅ H ₇ NO ₂ ), glutamic acid (C ₅ H ₉ NO ₄ ), aspartic acid (C ₄ H ₇ NO ₄ ), pyroglutamic acid (C ₅ H ₇ NO ₃ ), Hippuric acid (Hippuric acid, C ₉ H ₉ NO ₃ ) and mixtures thereof are selected from the group consisting of two, etchant composition. The etchant composition according to claim 1, further comprising 0.01 to 2% by weight of metal ions selected from the group consisting of iron ions, magnesium ions, copper ions, and mixtures thereof. The etchant composition of claim 1, wherein the etchant composition does not include a phosphate salt. The method of claim 10, wherein the content of the iron ion is 0.23 to 3.93% by weight based on 100% by weight of the iron and nitrate ions, the content of the copper ion is 0.34 to about 100% by weight of the copper ion and nitrate ion 5.76% by weight, with respect to 100% by weight of the magnesium ions and nitrates, the content of the magnesium ions is 0.16 to 2.79% by weight, the weight ratio of the iron ions and nitrates is 99: 1, the etchant composition. The etchant composition according to claim 7, further comprising 0.01 to 2% by weight of metal ions. The etchant composition according to any one of claims 1 to 13, wherein the etchant composition etches an ITO film, an Ag film or an alloy film thereof.

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