KR101299254B1 - Etching liquid composition - Google Patents

Abstract

According to the present invention, the etching liquid of various metal thin films and metal oxide thin films which does not contain oxygen, has no irritating odor, has little performance change, and can be used in the manufacturing process of electronic devices such as semiconductor devices and flat panel display devices. To provide a composition. Specifically, the etching liquid composition of this invention contains phosphoric acid, nitric acid, methoxyacetic acid, and water.

Description

Etching liquid composition {ETCHING LIQUID COMPOSITION}

1 is a view showing the variation of the components of the etching solution composition of Comparative Example 3;

FIG. 2 is a view showing component variation of the etching solution composition of Example 2. FIG.

[Technical Field]

This invention relates to the etching liquid composition used when etching a metal thin film and a metal oxide thin film in the manufacturing process of various electronic devices, such as a semiconductor device and a flat panel display apparatus.

BACKGROUND ART [0002]

In the manufacture of electronic devices, various metal thin films and metal oxide thin films are used, but aluminum and aluminum alloys have conventionally been used as wiring materials for semiconductor devices and as reflecting plates or reflecting electrode materials for liquid crystal displays.

In recent years, silver or an alloy mainly containing silver is used as a reflecting plate or a reflective electrode material of a liquid crystal display device, and indium tin oxide (ITO) and indium zinc oxide (IZO) are used as a transparent electrode material. As the etching liquid composition of the metal thin film and the metal oxide thin film used when forming these wirings, the reflecting plate, the reflecting electrode, or the transparent electrode, etc., in the case of the metal thin film of aluminum and aluminum alloy, the etching liquid composition conventionally consists of phosphoric acid, nitric acid, acetic acid, and water. (Hereinafter referred to as "mixed acids") are known.

On the other hand, in the case of a metal thin film containing silver as a main component, if the mixed acid used as the etching solution of aluminum and an aluminum alloy is used as it is, the etching rate may be increased and the controllability of etching may deteriorate. Is optimized for silver metal thin films (Patent Document 1: Japanese Patent Application Laid-Open No. 2004-176115) and in the case of a laminated film of ITO or IZO with a metal thin film such as silver or aluminum, the composition component ratio of the mixed acid is applicable. The patent application of the applicant of this invention which optimized for batch etching of laminated | multilayer film (patent document 2: Unexamined-Japanese-Patent No. 2004-1567070) is filed.

Moreover, the thing which optimized the etching rate by adding ethylene glycol or glycerin to a mixed acid for silver-based metal thin films is disclosed (patent document 3: Unexamined-Japanese-Patent No. 2002-231706).

In this way, the mixed acid is used as an etchant for the metal thin film and the metal oxide thin film. Nitric acid in the mixed acid mainly has a behavior of oxidizing the etching target material, acetic acid improves the wettability to the etching target material and controls the etching rate. It also acts as a moderator. For this reason, a mixed acid is an excellent etching liquid which can advance an etching by the etching rate which is controllable by optimizing the composition component ratio.

However, acetic acid in the mixed acid has a high volatility, so that the composition changes during the etching treatment and thus the stable etching performance is not maintained. It also has the problem of making it worse.

It is reported that an etching liquid composition similar to a mixed acid is composed of hydrofluoric acid, nitric acid, acetic acid, and water (Patent Document 4: Japanese Patent Laid-Open No. 5-102122), but also has the problem of odor by containing acetic acid. In order to control the etching rate, it is necessary to add hydrogen peroxide solution, which causes a problem of complicated operation.

In order to solve the problem of acetic acid odor, an etching liquid composition excluding acetic acid, i.e. phosphoric acid and nitric acid, has been reported as a component of the mixed acid, but nitric acid is appropriately added to the etching liquid composition for maintaining the etching rate. (Patent Document 5: Japanese Unexamined Patent Publication No. 2002-129361), or a process such as appropriately supplying hydrogen peroxide or nitric acid in the etching solution composition (Patent Document 6: Japanese Unexamined Patent Publication No. 49-45035). It is necessary and neither operation is complicated and practical. In addition, since the etching solution composition composed of phosphoric acid and nitric acid has low wettability, there is a problem such as an etching solution residue or side etching proceeds, which is unsuitable for processing a precise pattern.

Moreover, although the etching liquid composition which used citric acid instead of acetic acid which is a mixed acid composition component is disclosed (patent document 7: Unexamined-Japanese-Patent No. 10-130870), since citric acid has little wettability improvement effect, it has a fine pattern edge. edge) shape is not obtained and has problems such as causing etching residues. Moreover, although the said patent document discloses the etching liquid composition which adds urea in order to suppress generation | occurrence | production of NOx, the urea has the problem that the solubility with respect to an etching liquid composition is comparatively low, and the addition rate greatly suppresses an etching rate. It's happening.

Thus, the etching liquid composition which does not have the problem of an odor of acetic acid, is excellent in etching performance, is easy to handle, and practically excellent is not known until now.

That is, the subject of this invention is the etching liquid composition which can be used when etching a metal thin film in the manufacturing process of various electronic devices, such as a semiconductor device and a flat panel display apparatus, and there is no problem of a bad smell, and stable etching performance It is providing the etching liquid composition which can hold | maintain.

In order to solve the above-mentioned problems, it has the stability and miscibility with respect to phosphoric acid and nitric acid, and there is no problem of bad smell, and when it mix | blends with phosphoric acid and nitric acid, it gives the etching performance at least equivalent to mixed acid. The etching liquid composition using the organic acid which can be used, ie, the etching liquid composition which mix | blended organic acid other than acetic acid, phosphoric acid, and nitric acid, was considered as a means to solve this problem.

Of these organic acids, methoxyacetic acid can be mixed with phosphoric acid and nitric acid at any ratio, and has no irritating odor and is liquid at room temperature, so that it is not precipitated in the vicinity of the liquid surface of the etching bath and in the pipe. It is confirmed that it is possible to increase the wettability to the surface, and that the etching rate control effect comparable to acetic acid is confirmed, and that the composition composed of phosphoric acid, nitric acid, methoxyacetic acid and water is an etching solution composition that can solve the present problem. As a result of further research, the present invention was completed.

That is, this invention relates to the said etching liquid composition containing phosphoric acid, nitric acid, methoxyacetic acid, and water in the etching liquid composition which etches a metal thin film.

Moreover, in this invention, it is preferable that the amine compound is further mix | blended in the said etching liquid composition.

Moreover, in this etching liquid composition, it is preferable that the said amine compound is 1 type, or 2 or more types chosen from glycine, aspartic acid, and imino diacetic acid.

Moreover, in this invention, it is preferable that the said metal thin film is silver or a silver alloy thin film in the said etching liquid composition.

Moreover, it is preferable that this invention contains 4-9 mol / L phosphoric acid, 0.1-2 mol / L nitric acid, 2-7 mol / L methoxyacetic acid, and water in the said etching liquid composition.

In addition, in the said etching liquid composition, this invention WHEREIN: 4-9 mol / L phosphoric acid, 0.1-2 mol / L nitric acid, 2-7 mol / L methoxyacetic acid, and the 1 type, or 2 or more types of an amine compound are added together, It is preferable to mix | blend 0.05-1 mol / L and water.

[ Carrying out the invention  Best form for

EMBODIMENT OF THE INVENTION Below, embodiment of this invention is described in detail.

The etching liquid composition of this invention contains phosphoric acid, nitric acid, methoxyacetic acid, and water, It is characterized by the above-mentioned.

In the etching liquid composition of this invention, the compounding quantity of phosphoric acid and nitric acid is suitably determined from a viewpoint of the range which can be etched with few side etching with high precision, especially an etching rate, an etching residue, and generation of an etching nonuniformity. When the etching rate is high, the etching activity is good, but a large amount of bubbles are generated during the etching reaction, which may cause etching unevenness. Therefore, when the metal thin film to be etched is a silver or silver alloy thin film, the compounding amount of phosphoric acid is preferably 4 to 9 mol / l, more preferably 5 to 8 mol / l, and the compounding amount of nitric acid is preferably 0.1 to 2 mol / l, more preferably 0.3 to 1.5 mol / l. On the other hand, it is preferable to make the compounding quantity of methoxyacetic acid into the range which can hold | maintain an etching rate in a fixed range, and does not produce problems, such as an etching residue and pattern edge shape unevenness. From these viewpoints, the compounding quantity of methoxyacetic acid becomes like this. Preferably it is 2-7 mol / l, More preferably, it is 3-6 mol / l.

It is possible to add a NOx inhibitor suitably to the etching liquid composition of this invention. The NOx inhibitor to be added is not particularly limited as long as it has a NOx inhibitory effect, but an amine compound is preferable, and urea, glycine, aspartic acid, iminodiacetic acid, and the like are typically mentioned. In particular, glycine, aspartic acid, and imino diacetic acid are preferable because of high solubility in mixed acids containing phosphoric acid, nitric acid, methoxyacetic acid and water, and low etching inhibition. The amine compound to mix may be 1 type, or may be mix | blended 2 or more types in combination. The compound of the amine compound is appropriately selected in consideration of the solubility in the phosphoric acid, nitric acid, methoxyacetic acid and water, the etching inhibiting property, and the like.

When adding an amine compound, the addition amount is adjusted in consideration of the NOx inhibitory effect and the etching rate. Moreover, since the solubility of the amine compound in an etching liquid composition changes with the compounding ratio of phosphoric acid, nitric acid, methoxyacetic acid, and water, it is preferable to adjust the addition amount in consideration of the viscosity. In addition, when there is much silver etching amount, it is preferable to add many amine compounds.

When one type of amine compound is used, when the etching amount of silver is 4 g / l, glycine is 0.2 mol / l or more, aspartic acid is 0.1 mol / l or more, and imino diacetic acid is 0.05 mol / l or more. Is admitted. The upper limit of these amine compounds is preferably 1 mol / l or less, more preferably 0.5 mol / l or less. When using two or more types of amine compounds, when the etching amount of silver is 4 g / L, Preferably it is 0.05-1 mol / L, More preferably, it is 0.1-0.5 mol / L.

About the temperature which etches with the etching liquid composition of this invention, the etching rate may be low at low temperature, the etching utility time may become too long, while the etching rate is high at high temperature, the controllability of etching is considered, etc. The temperature is preferably 20 to 40 ° C.

Moreover, in order to improve the wettability with respect to the etched thin film surface, you may contain surfactant. As surfactant, a nonionic system is preferable.

In addition, the etching liquid composition of this invention selects the compounding quantity of phosphoric acid, nitric acid, methoxyacetic acid, and water suitably, and it is an alloy which has metals, such as aluminum, silver, copper, molybdenum, nickel, and each metal as a main component, and ITO, IZO. It can be used as an etching solution of a thin film made of metal oxides such as these. Here, the alloy which has silver as a main component is silver (Ag) -palladium (Pd), Ag-Pd-copper (Cu), or Ag- neodium (Nd) -Cu typically.

Moreover, the etching liquid composition of this invention can suppress generation | occurrence | production of excess of NOx by selecting suitably the kind and compounding quantity of an amine compound, and mix | blending.

[ Example ]

Although an Example and a comparative example are given to the following and this invention is demonstrated in more detail, these do not limit this invention at all. In addition, the etching rate described below employ | adopted the numerical value when the etching operation was performed several times with the same liquid, and reached the stable etching rate.

[Evaluation test 1] Methoxyacetic acid  effect

In order to confirm the effect of methoxyacetic acid as an acetic acid substitute, phosphoric acid / nitric acid in a composition consisting of 6.0 mol / l phosphoric acid, 1.0 mol / l nitric acid and water and 5.0 mol / l of acetic acid or methoxyacetic acid added thereto The results of comparing the solubility in the system and the etching rate (etching material: pure silver foil (2 cm each, thickness 50 μm), liquid temperature: 30 ° C., 1 minute after reaching a stable etching rate, etc.) are shown in the following table. Marked at 1.

By this, it was confirmed that methoxyacetic acid has the advantages of an etching rate control effect similar to acetic acid, good solubility in phosphoric acid / nitric acid system, and no stimulating odor.

Furtherance Solubility Etching speed
(Nm / min) Irritating smell Comparative Example 1 Phosphoric Acid / Nitric Acid - 590 none Comparative Example 2 Phosphoric Acid / Nitric Acid / Acetic Acid ○ 1060 has exist Example 1 Phosphoric Acid / Nitric Acid / Methoxyacetic Acid ○ 840 none

[Evaluation Test 2] The amount of the etching liquid composition kills

Composition consisting of 6.0 mol / l phosphoric acid, 0.6 mol / l nitric acid, 7.0 mol / l acetic acid and water (Comparative Example 3), 6.0 mol / l phosphoric acid, 0.9 mol / l nitric acid, 5.0 mol / l methoxyacetic acid and water Using the composition (Example 2), the solution was left to stand for 24 hours at a liquid temperature of 30 ° C. and agitation conditions, and the results of analyzing the components of each composition by capillary electrophoresis every 8 hours were shown in Table 3, FIGS. 1 and FIG. 2 is shown.

In phosphoric acid / nitric acid / acetic acid system, acetic acid is greatly reduced by volatilization, and phosphoric acid and nitric acid are greatly concentrated. Phosphoric acid / nitric acid / acetic acid system is not able to maintain the initial performance due to large component fluctuations, it is obvious that long-term use is impossible.

On the other hand, in the phosphoric acid / nitric acid / methoxyacetic acid system, there is a slight concentration tendency, but the variation is small compared with the phosphoric acid / nitric acid / acetic acid system. The concentration of each component is mainly due to the volatilization of water, so that water can be recovered by replenishing water. As described above, the phosphoric acid / nitric acid / methoxyacetic acid system was confirmed to have a lower compositional variation than the conventional phosphoric acid / nitric acid / acetic acid system and was a composition suitable for long-term use.

Furtherance mol / ℓ Phosphoric Acid nitric acid Acetic acid Methoxyacetic acid Phosphoric Acid / Nitric Acid / Acetic Acid (Comparative Example 3) 6.0 0.6 7.0 - Phosphoric Acid / Nitric Acid / Methoxyacetic Acid (Example 2) 6.0 0.9 - 5.0

Furtherance ingredient Change in content (%) Early 8 hours later 16 hours later 24 hours later Phosphoric Acid / Nitric Acid / Acetic Acid
(Comparative Example 3) Phosphoric Acid 100.0 111.3 122.1 132.2 nitric acid 100.0 109.6 118.9 125.1 Acetic acid 100.0 89.0 77.9 66.4 Phosphoric Acid / Nitric Acid / Methoxyacetic Acid
(Example 2) Phosphoric Acid 100.0 102.0 107.2 109.8 nitric acid 100.0 101.2 104.4 105.5 Metoxaacetic acid 100.0 101.7 107.1 109.1

[Evaluation test 3] Processing performance of etching liquid composition

In a composition consisting of 7.0 mol / l phosphoric acid, 0.5 mol / l nitric acid and water (Comparative Example 4), and a composition in which 5.0 mol / l of acetic acid or methoxyacetic acid was added thereto (Comparative Examples 5 and 3), liquid temperature 30 After 1 degreeC and stable etching rate were reached, the etching rate of pure silver foil (2 cm square, 50 micrometers in thickness) was measured on unstirred conditions for 1 minute. Moreover, after preparing the glass substrate which formed the resist pattern on the silver alloy (Ag-Pd-Cu) film | membrane of thickness 200nm, using the said 3 types of etching liquid composition, after reaching the liquid temperature of 30 degreeC and the stable etching rate, The etching process was performed under the correct etching time and unstirred conditions. These results are shown in Table 5 below.

As a result, the etching rate of pure silver foil in the phosphoric acid / nitric acid system was 240 nm / min. In the etching state of the silver alloy substrate, the side etching was as large as 4.0 µm, and the pattern edge shape was also rough, which was poor. On the other hand, in the phosphoric acid / nitric acid / acetic acid system, phosphoric acid / nitric acid / methoxyacetic acid, the etching rate of pure silver foil is 850 nm / min, 700 nm / min, respectively, and the etching state of a silver alloy substrate has little side etching, The pattern edge shape was also smooth, and the favorable etching state was obtained.

As described above, in the etching liquid composition in which acetic acid or methoxyacetic acid is added to the phosphoric acid / nitric acid system, the etching rate and the etching state of the silver alloy substrate are improved compared to the no additive system, and methoxyacetic acid is equivalent to acetic acid or more. It confirmed that it represents.

Furtherance mol / ℓ Phosphoric Acid nitric acid Acetic acid Methoxyacetic acid Phosphoric Acid / Nitric Acid (Comparative Example 4) 7.0 0.5 - - Phosphoric Acid / Nitric Acid / Acetic Acid (Comparative Example 5) 7.0 0.5 5.0 - Phosphoric Acid / Nitric Acid / Methoxyacetic Acid (Example 3) 7.0 0.5 - 5.0

Furtherance Etching Speed (nm / min) Pattern Edge Shape Side etching (μm) Phosphoric Acid / Nitric Acid (Comparative Example 4) 240 Roughness 4.0 Phosphoric Acid / Nitric Acid / Acetic Acid (Example 5) 850 lubricity 1.5 Phosphoric Acid / Nitric Acid / Methoxyacetic Acid (Example 3) 700 lubricity 1.1

Evaluation Test 4 Effect by Addition of Amine Compound

A liquid when each amine compound is added in various amounts in a gas composition composed of 6.0 mol / l phosphoric acid, 1.0 mol / l nitric acid, 5.0 mol / l methoxyacetic acid, and water, and the silver is dissolved in 4 g / L and then sealed and stored. The stability was evaluated. The results are shown in Table 6 below.

Stability of the etching liquid composition after sealing storage for 1 week becomes favorable by adding 0.2 mol / L of glycine, 0.1 mol / L of aspartic acid, and 0.05 mol / L of imino diacetic acid.

Amine compound Addition amount
(mol / ℓ) Liquid stability
(After 1 week) Example 4 Glycine 0.2 ○ Example 5 Aspartic acid 0.1 ○ Example 6 0.2 ○ Example 7 Iminodiacetic acid 0.05 ○ Example 8 0.1 ○ Example 9 0.2 ○

Liquid stability: ○ Good

[Evaluation test 5] effect of the amine compound on the etching rate

About the etching rate of the composition which added 0.5 mol / L of each amine compound to the gas composition which consists of 6.0 mol / L of phosphoric acid, 1.0 mol / L of nitric acid, 5.0 mol / L of methoxyacetic acid, and water, under the same conditions as the evaluation test 1 The evaluation results are shown in Table 7 below.

Examples 10-12 to which glycine, aspartic acid or imino diacetic acid were added did not have a drastic fall of the etching rate, and the preferable etching rate equivalent to Example 1 was obtained.

Amine compound Etching Speed (nm / min) Example 10 Glycine 600 Example 11 Aspartic acid 590 Example 12 Iminodiacetic acid 420 Example 1 No additives 840

[Evaluation test 6] concentration range of nitric acid

Table 8 shows the results of evaluation under the same conditions as in Evaluation Test 1 in the composition of which was fixed at 6.0 mol / l of phosphoric acid, 5.0 mol / l of methoxyacetic acid and 0.2 mol / l of glycine, and the amount of phosphoric acid compound was changed. The etching rate of phosphoric acid / nitric acid / methoxyacetic acid / glycine system can be freely adjusted according to the amount of nitric acid blended.

Compounding amount (mol / ℓ) Etching rate
(Nm / min) Phosphoric Acid nitric acid Methoxyacetic acid Glycine Example 13 6.0 0.6 5.0 0.2 390 Example 14 6.0 0.8 5.0 0.2 590 Example 4 6.0 1.0 5.0 0.2 760 Example 15 6.0 1.2 5.0 0.2 930

[Evaluation test 7] concentration range of phosphoric acid

Table 9 shows the results of evaluation under the same conditions as in Evaluation Test 1 with respect to the etching rate in the composition which fixed at 1.0 mol / l nitric acid, 5.0 mol / l methoxyacetic acid, 0.2 mol / l glycine, and changed the amount of phosphoric acid mix. Mark on. The etching rate of phosphoric acid / nitric acid / methoxyacetic acid / glycine system can be freely adjusted by the phosphoric acid compounding amount.

Compounding amount (mol / ℓ) Etching rate
(Nm / min) Phosphoric Acid nitric acid Methoxyacetic acid Glycine Example 16 4.0 1.0 5.0 0.2 100 Example 4 6.0 1.0 5.0 0.2 760 Example 17 7.0 1.0 5.0 0.2 1060

[Evaluation test 8] Methoxyacetic acid  Concentration range

The results of evaluating the etching rate in the composition in which phosphoric acid was fixed at 6.0 mol / l, nitric acid at 1.0 mol / l, and glycine at 0.2 mol / l and the methoxyacetic acid compounding amount was changed were evaluated under the same conditions as in Evaluation Test 1. Mark 10. Although the etching rate of phosphoric acid / nitric acid / methoxyacetic acid / glycine system can be controlled to some extent by the methoxyacetic acid compounding amount, the effect is mild compared with phosphoric acid or nitric acid.

Compounding amount (mol / ℓ) Etching rate
(Nm / min) Phosphoric Acid nitric acid Methoxyacetic acid Glycine Example 19 6.0 1.0 1.0 0.2 400 Example 20 6.0 1.0 3.0 0.2 600 Example 2 6.0 1.0 5.0 0.2 760 Example 21 6.0 1.0 6.0 0.2 760

[Evaluation test 9] Silver, etching of silver alloy

In the etching solution composition of Example 6, consisting of 6.0 mol / l phosphoric acid, 1.0 mol / l nitric acid, 5.0 mol / l methoxyacetic acid, 0.2 mol / l glycine, and water, a liquid temperature of 30 ° C., 1 minute after reaching a stable etching rate The etching rate of pure silver foil (2 cm each, 50 micrometers in thickness) was measured on unstirred conditions, and the etching rate was 760 nm / min.

A glass substrate on which a resist pattern was formed was prepared on a silver alloy (Ag-Pd-Cu) film having a thickness of 200 nm, using an etching solution composition of Example 6, a liquid temperature of 30 ° C., a stable etching rate time, and no stirring condition. Etching was performed.

The exact etching time was determined by confirming that there was no residue with an optical microscope. As a result, there was no side etching, the pattern shape was smooth, and the favorable etching state without the etching residue was obtained.

NOx did not generate | occur | produce during the etching process and the storage after use, The said etching liquid composition was favorable, liquid stability was good, it can be used repeatedly, and it was excellent in storage stability.

[Evaluation Test 10] Silver alloy  etching

An etching test was carried out under the same conditions as in Evaluation Test 9, except that the etching solution composition of Example 6 consisting of 6.0 mol / l phosphoric acid, 1.0 mol / l nitric acid, 5.0 mol / l methoxyacetic acid, 0.2 mol / l aspartic acid, and water was used. It was.

As a result, the etching rate in pure silver foil was 820 nm / min. In the silver alloy / glass substrate, there were few side etching, the pattern edge shape was smooth, and there was no etching residue, and the favorable etching state was obtained.

The etching liquid composition did not generate NOx during the etching treatment and during storage after use, and the liquid stability was good, it was repeatedly usable, and the storage stability was excellent.

[Evaluation Test 11] Silver alloy  etching

Etching test under the same conditions as Evaluation Test 9 except for using the etching solution composition of Example 9, which was composed of 6.0 mol / l of phosphoric acid, 1.0 mol / l of nitric acid, 5.0 mol / l of methoxyacetic acid, 0.2 mol / l of iminodiacetic acid, and water. Was performed.

As a result, the etching rate in pure silver foil was 670 nm / min. In the silver alloy / glass substrate, there were few side etching, the pattern edge shape was also smooth, and there was no etching residue, and the favorable etching state was obtained.

The etching liquid composition did not generate NOx during the etching treatment and during storage after use, and the liquid stability was good, it was repeatedly usable, and the storage stability was excellent.

From the etching evaluation test of the said silver alloy, the etching compound composition which mix | blends phosphoric acid, nitric acid, methoxyacetic acid, and water is further mix | blended with the amino compound which consists of 1 type (s) or 2 or more types chosen from glycine, aspartic acid, and imino diacetic acid. The etching liquid composition was confirmed to have good etching performance and liquid stability with respect to silver and silver alloy.

As can be seen from the above description, the etching liquid composition of the present invention is a novel etching liquid composition in which acetic acid, which is a composition component in a mixed acid that is a conventional etching solution, is replaced with methoxyacetic acid, and has no irritating odor. Since methoxyacetic acid, which is a liquid at room temperature, has a function of enhancing wettability similarly to acetic acid, the composition has excellent pattern edge shape and the like, and has etching performance equivalent to that of mixed acid. In the conventional acetic acid system, there is a tendency that stable performance cannot be maintained due to component fluctuations due to volatilization of acetic acid. However, in the present invention, methoxy acetic acid is used instead of this, so there is no such problem. This is long.

In addition, by adding an amine compound such as glycine to the composition, it is possible to prevent the liquid from turning blue or foaming when it is kept closed after the etching treatment or when a large amount of etching treatment is performed in a short time. Moreover, since the increase of an etching rate can be suppressed, the usability further improves. This is considered to be due to the NOx inhibitory effect of the amine compound reacting with excess NOx (especially NO ₂ ⁻ ) that accumulates in the system.

In addition, the etching liquid composition which concerns on this invention is used as etching liquid of various metal thin films and metal oxide thin films at the time of forming wiring, an electrode, a reflecting plate, etc. in manufacturing processes of electronic devices, such as a semiconductor device and a flat panel display apparatus. It is possible.

Claims (6)

An etching liquid composition for etching a metal thin film, wherein the etching liquid composition contains 4 to 9 mol / l phosphoric acid, 0.1 to 2 mol / l nitric acid, 2 to 7 mol / l methoxyacetic acid, and water. The etching liquid composition of Claim 1 in which 0.05-1 mol / L was further mix | blended in total of 1 type, or 2 or more types of an amine compound. The etching liquid composition according to claim 2, wherein the amine compound is one or two or more selected from glycine, aspartic acid and imino diacetic acid. The etching liquid composition according to any one of claims 1 to 3, wherein the metal thin film is a silver or silver alloy thin film. delete delete

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