TW201514342A - Etchant composition for copper and molybdenum containing film - Google Patents

Abstract

This invention relates to an etchant composition which can, during etching of a copper and molybdenum containing film, increase the copper film etching rate even if the copper film has a greater thickness, maintain a high etching rate for a molybdenum containing film, and prevent poor wiring sections. The etchant composition is an etchant composition for copper and molybdenum containing film and comprises hydrogen peroxide as the oxidant and persulfate, characterized in that it comprises 0.5 to 10 parts by weight of persulfate relative to 100 parts by weight of hydrogen peroxide.

Description

Etching solution composition containing copper and molybdenum containing film

The present invention relates to an etching liquid composition of a copper-molybdenum film or a copper-molybdenum containing film (hereinafter referred to as "copper/molybdenum containing film"), in particular, an etching liquid composition for a copper and molybdenum containing film of a TFT-LCD display electrode. .

A microcircuit such as a semiconductor device, a TFT-LCD, or an OLED is uniformly coated on a conductive metal film such as aluminum, aluminum alloy, copper, or copper alloy formed on a substrate, or an insulating film such as a hafnium oxide film or a tantalum nitride film. The photoresist is then imaged by light-irradiated film, and the desired pattern photoresist is imaged, and is displayed on the metal film or the insulating film under the photoresist by dry etching or wet etching. After the pattern, it is completed by stripping off a series of lithography processes such as unnecessary photoresist.

The copper alloy used for the gate of the large display and the data metal wiring has lower impedance and no environmental problems than the aluminum-chromium wiring in the prior art. Since copper has a low adhesion to a glass substrate and an insulating film and is easily diffused into a ruthenium oxide film, titanium, molybdenum or the like is generally used as the lower film metal.

In the case of simultaneously etching a copper film and a molybdenum-containing film, as a related art of a usable etching liquid composition, hydrogen peroxide is disclosed in Korean Patent Laid-Open Publication No. 2006-0064881, Japanese Patent Publication No. 2006-0099089, and the like. The base copper/molybdenum contains an etchant for the film. However, when these etching liquids are repeatedly etched, the metal content in the etching liquid increases, and the stone etching characteristics such as etching cone angle, etching deviation, and etching straightness are lost. To reduce the metal content in the etching liquid, a large amount is required. The etching solution is a problem of the prior art.

Further, the high image quality and large size of the display increase the thickness of the copper metal used for wiring, and the pursuit of high image quality requires that the picture element become smaller, the wiring width increases, and the resistance of the wiring needs to be reduced. In this regard, the thickness of the copper metal used for wiring has to be increased.

When the thickness of the copper metal is increased, the etching process time becomes long, and the production efficiency is lowered. If the etching speed is to be increased, the wiring section is defective, and problems may occur.

Advanced technical literature Patent literature

(Patent Document 1) Patent Publication No. 2006-0064881 (published on June 14, 2006)

(Patent Document 2) Patent Publication No. 2006-0099089 (published on September 19, 2006)

An object of the present invention is to provide an etching liquid composition which can maintain a high etching rate even when the copper/molybdenum-containing film is etched, and which can maintain a high etching rate and ensure a construction time without a defect in wiring segments.

In order to achieve the object of the present invention, the copper and molybdenum of the present invention comprise a film etching solution composition, which is an etching liquid composition containing a copper and molybdenum containing film of hydrogen peroxide and persulfate as an oxidizing agent. It is characterized in that it contains 0.5 to 10 parts by weight of the persulfate with respect to 100 parts by weight of the hydrogen peroxide.

According to a preferred embodiment of the present invention, 15 to 30% by weight of hydrogen peroxide, 0.05 to 3% by weight of persulfate, 0.1 to 3% by weight of etching inhibitor, 0.1 to 5 by weight, based on the total weight of the composition. % chelating agent, 0.01 to 2% by weight of one or more compounds selected from the group consisting of inorganic acids, organic acids and salts thereof, 0.01 to 2% by weight of fluoride, and the total weight of the composition is 100% by weight Water.

The persulphate is selected from the group consisting of sodium persulfate, potassium persulfate, ammonium persulfate, and mixtures thereof.

The inhibitor is selected from the group consisting of furan, thiophene, pyrrole, oxazole, imidazole, pyrazole, 1,2,4-triazole, tetrazole, 5-aminotetrazole, methyltetrazole, pyridazine, methylhydrazine Oxazine, hydroxyethyl hydrazine Pyrazine, pyrrolidine and alloxan, oxonium, benzothiophene, anthracene, benzimidazole, benzopyrazole, aminotetrazole, methylbenzotriazole, hydromethylbenzotriazole, methylol a group of benzotriazoles and mixtures thereof.

The chelating agent is a compound containing a carboxylic acid group or a phosphoric acid group together with an amino group in the molecule.

Further, the chelating agent is selected from the group consisting of iminodiacetic acid, ammonia triacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, aminotrimethylenephosphonic acid, 1-hydroxyethylidene-1,1-diphosphate. a group consisting of ethylenediaminetetramethylphosphoric acid, diethylenetriaminepentamethylenephosphoric acid, alanine, glutamic acid, aminobutyric acid, and glycine, and mixtures thereof.

The additive is selected from the group consisting of inorganic acids containing sulfuric acid, nitric acid, phosphoric acid, hydrochloric acid and hydrofluoric acid, and contains acetic acid, formic acid, butyric acid, citric acid, glycolic acid, oxalic acid, malonic acid, valeric acid, propionic acid, tartaric acid, and glucose. A group of organic acids of acid, glycine, succinic acid, and salts thereof and mixtures thereof.

The etching additive is selected from the group consisting of sulfates consisting of potassium hydrogen sulfate, sodium hydrogen sulfate, sodium sulfate, potassium sulfate, ammonium sulfate, and mixtures thereof.

The fluoride is a compound that dissociates F- or HF2-.

The fluoride is selected from the group consisting of hydrazine, sodium fluoride, potassium fluoride, aluminum fluoride, borofluoric acid, ammonium fluoride, ammonium hydrogen fluoride, sodium hydrogen fluoride, potassium fluorohydride, ammonium fluoroborate, and mixtures thereof.

The water is deionized water having a specific resistance of 18 M?/cm or more.

Also included are additives selected from the group consisting of hydrogen peroxide stabilizers, etch stabilizers, glass etch inhibitors, and mixtures thereof.

Other embodiments related to the present invention are described in detail in the following detailed description.

The invention has the beneficial effects that when the copper/molybdenum containing film used for the TFT-LCD display electrode is etched according to the etching liquid composition of the present invention, the etching speed of the copper film can be maintained at 140 Å/s or more, and the molybdenum containing film is etched. The speed is 15 Å/s or more, which can control the occurrence of defective wiring segments.

1 is a photograph of a cross section of a test piece observed by a scanning electron microscope after etching a copper/molybdenum film by the etching liquid composition according to Embodiment 1 of the present invention; FIG. 2 is an etching liquid combination using Comparative Example 1 of the present invention. A photograph of a cross section of a test piece observed by a scanning electron microscope after etching a copper/molybdenum film; and FIG. 3 is a scanning of a copper/molybdenum film by etching the composition of Comparative Example 3 of the present invention. A photograph of the cross section of the test piece observed by an electron microscope.

The present invention may be embodied in a variety of forms, and the embodiments in the present specification are only for describing the features of the present invention in detail, and the present invention is not limited thereto, but is within the scope of the technical idea and the spirit of the present invention. Changes, substitutions, modifications, and the like are within the scope of protection of the present invention. In the description of the present invention, well-known techniques are not described in detail in order to prevent the description of the core technical features of the present invention.

Hereinafter, the etching liquid composition of the copper/molybdenum containing film according to the embodiment of the present invention will be described in detail.

The etching liquid composition of the present invention can simultaneously etch a copper/molybdenum containing film. The "copper/molybdenum alloy film" herein means a copper film and a molybdenum alloy film, and the molybdenum alloy is an alloy of molybdenum and various metals, preferably an alloy with titanium, tantalum, chromium, niobium, nickel, indium or tin, more preferably Alloy with titanium.

The etching liquid composition of the present invention is an etching liquid composition containing a copper and molybdenum containing film as hydrogen peroxide and persulfate as an oxidizing agent, and contains 0.5 to 10 parts by weight based on 100 parts by weight of the hydrogen peroxide. Said persulfate.

In the hydrogen peroxide etching solution composition, in order to increase the etching rate of the thick copper wiring, hydrogen peroxide is used as a single oxidizing agent, and when it exceeds 30% by weight, it is difficult to control the decomposition reaction of the etching liquid, and it is difficult to eliminate the wiring section. Bad. In the present invention, by using two kinds of oxidizing agents at the same time, the wiring section can be reduced while the etching rate is increased.

According to a preferred embodiment of the present invention, 15 to 30% by weight of hydrogen peroxide, 0.05 to 3% by weight of persulfate, 0.1 to 3% by weight of etching inhibitor, 0.1 to 5 by weight, based on the total weight of the composition. % chelating agent, 0.01~2% by weight selected from inorganic acids, organic acids and One or more compounds in the group consisting of salts, 0.01 to 2% by weight of fluoride, and 100% by weight of water based on the total weight of the composition.

Next, each constituent component of the etching liquid composition of the copper/molybdenum containing film according to the embodiment of the present invention will be described in detail.

a) Hydrogen peroxide

In the etching liquid composition of the present invention, hydrogen peroxide is used as a main oxidant of copper, molybdenum or a molybdenum alloy.

The above hydrogen peroxide may be contained in an amount of 15 to 30% by weight based on the total weight of the etching solution composition. When the amount is less than 15% by weight, the oxidation of the copper-molybdenum alloy is insufficient, and etching cannot be achieved. When the amount exceeds 30% by weight, the etching rate is too fast, and it is difficult to control the progress of the process. A suitable etching rate can prevent etching residue and etching defects, reduce etching deviation, and facilitate adjustment work, and it is preferable that the content of hydrogen peroxide is 20 to 30% by weight.

b) Persulfate

According to the etching liquid composition of the present invention, the persulfate is selected from the group consisting of sodium persulfate, potassium persulfate, ammonium persulfate and a mixture thereof, but is not limited thereto.

When the content of the persulfate is less than 0.5 part by weight based on 100 parts by weight of hydrogen peroxide, the etching rate is a copper film etching rate of 140 Å/s or more, and the etching rate of the molybdenum containing film is difficult to reach 15 Å/s; This will result in an undesirable increase in wiring segments. Thus, it is preferred that the persulfate content is from 0.5 to 10 parts by weight, more preferably from 0.5 to 8 parts by weight or from 0.5 to 7 parts by weight, per 100 parts by weight of the hydrogen peroxide.

c) etching inhibitor

In the etching liquid composition of the present invention, the etching inhibitor can adjust the etching speed of copper, molybdenum or molybdenum alloy, reduce etching deviation, improve engineering efficiency, and have an etching profile with an appropriate etching cone angle.

Specifically, the etching inhibitor may be a monocyclic hetero atom compound containing at least one or more of oxygen, sulfur and nitrogen in the molecule, or a composite compound of a monocyclic hetero atom and a benzene ring condensation structure. . The above monocyclic hetero atom compound may be a heterocyclic aromatic compound having a monocyclic structure of 1 to 10 carbons, or may be a heterocyclic aliphatic compound. Specifically, it can be furan, thiophene, Heterocyclic aromatic compounds such as pyrrole, oxazole, imidazole, pyrazole, 1,2,4-triazole, tetrazole, oxindole; pyridazine, methylpyrazine, hydroxyethylpyrazine, pyrrolidine and tetra A heterocyclic aliphatic compound such as oxypyrimidine; not limited thereto. Further, the composite compound having a monocyclic hetero atom and a benzene ring condensation structure containing at least one or more of oxygen, sulfur and nitrogen in the molecule may be pyridazine, methylpyrazine, hydroxyethylpyrazine or pyrrolidine. And alloxan and the like are not limited thereto. It is also possible to use one of the above compounds alone or in combination of two or more of the above compounds.

The above etching inhibitor is contained in an amount of from 0.1 to 3% by weight, preferably from 0.1 to 2% by weight, based on the total mass of the etchant composition. When the etching inhibitor is less than 0.1% by weight, it is difficult to adjust the etching rate, the adjustment of the etching cone angle can be lowered, the engineering efficiency is low, and mass production cannot be achieved; if it exceeds 3% by weight, the etching rate is slowed and the efficiency is inefficient.

d) chelating agent

The chelating agent in the etching liquid composition of the present invention forms a chelate and deactivates copper and molybdenum alloy ions during etching to suppress decomposition reaction of hydrogen peroxide in the etching solution. If no chelating agent is added to the etching liquid composition of the present invention, the acidified metal ions cannot be deactivated during the etching process, which promotes the decomposition reaction of hydrogen peroxide in the etching liquid composition, which may result in Fever and explosion.

A chelating agent is a compound containing a carboxylic acid group or a phosphoric acid group together with an amino group in a molecule. It can be iminodiacetic acid, ammonia triacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, aminotrimethylenephosphonic acid, 1-hydroxyethylidene-1,1-diphosphate, ethylenediaminetetra The phosphoric acid, diethylenetriamine pentamethylidene phosphate, alanine, glutamic acid, aminobutyric acid, glycine, and the like may be used alone or in combination of two or more of them.

The content is preferably from 0.1 to 5% by weight, more preferably from 0.1 to 3% by weight, based on the total weight of the whole composition. When it is less than 0.1% by weight, the amount of inactivated metal ions is small, so that the effect of suppressing the decomposition reaction of hydrogen peroxide is weakened; if it exceeds 5% by weight, excessive chelation is formed to cause metal ions. The effect of inactivation is not good and affects engineering efficiency.

e) Etching additives

The etch additive acts as an auxiliary copper oxide, molybdenum, and molybdenum alloy to improve the etch profile. The etching additive may be a mineral acid, an organic acid or a salt thereof, and may be one type or a mixture of two types. on.

Specifically, the inorganic acid is sulfuric acid, nitric acid, phosphoric acid, hydrochloric acid and hydrofluoric acid; the organic acid is acetic acid, formic acid, butyric acid, citric acid, glycolic acid, oxalic acid, malonic acid, valeric acid, propionic acid, tartaric acid, glucose Acid, glycine, succinic acid; the above salts refer to salts of the above organic acids and inorganic acids.

In particular, the sulfate is potassium hydrogen sulfate, sodium hydrogen sulfate, sodium sulfate, potassium sulfate, ammonium sulfate or the like.

The content of the above etching additive is 0.1 to 5% by weight, preferably 0.1 to 3% by weight based on the total amount of the etching liquid composition, and when less than 0.1% by weight, the effect of using an etching solution to improve the etching profile is small; when it exceeds 5% by weight Excessive etching additives can cause a decrease in etching characteristics.

f) fluoride

When the fluoride in the etching liquid composition of the present invention is simultaneously etched in the copper-molybdenum alloy, the etching rate of the molybdenum alloy can be increased, the length of the tail can be reduced, and the molybdenum alloy residue generated during etching can be removed. If the tail of the molybdenum alloy is increased, the brightness will be lowered, and if the residue remains on the substrate and the lower film, electrical short-circuit, poor wiring, and reduced brightness will be caused, so the residue must be removed.

The fluoride of the present invention is a compound which decomposes F- or HF2- ions, and may be hydrazine, sodium fluoride, potassium fluoride, aluminum fluoride, borofluoric acid, ammonium fluoride, ammonium hydrogen fluoride, sodium hydrogen fluoride or potassium hydrogen fluoride. Further, one or two or more kinds of the above-mentioned fluorides may be used together with ammonium fluoroborate or the like.

The fluoride is preferably present in an amount of from 0.01 to 2% by weight, more preferably from 0.01 to 1% by weight, based on the total weight of the whole composition. When it is less than 0.01% by weight, the residue of the molybdenum alloy cannot be effectively removed, and if it exceeds 2% by weight, the lower film is etched.

g) water

The water used in the etching liquid composition of the present invention is not particularly limited, and it is preferable to use deionized water, and it is more preferable to use deionized water having a specific resistance value of 18 MΩ/cm or more after removing ions using water. The above water content is such that the total weight of the etching liquid composition reaches 100% by weight.

h) other additives

In the copper/molybdenum containing film-containing etching liquid composition of the present invention, in order to improve the etching performance, any one of the additives used in the etching liquid composition may be selected. The additive may be a hydrogen peroxide additive, an etch stabilizer, a glass etch inhibitor, or the like. It may be used in combination of one kind or two or more kinds.

The hydrogen peroxide stabilizer can control the hydrogen peroxide decomposition reaction when the content of the metal ions in the etching liquid is increased when the etching process is repeated. Specifically, the hydrogen peroxide stabilizer may use a phosphate, a dihydric alcohol, an amine or a mixture thereof.

When the hydrogen peroxide stabilizer is included in the etching solution composition, the content thereof is from 0.1 to 5% by weight, preferably from 0.5 to 3% by weight, based on the total weight of the composition. When the amount of the hydrogen peroxide stabilizer is less than 0.1% by weight, the effect of controlling the hydrogen peroxide reaction is small, and when it exceeds 5% by weight, the etching performance is lowered.

When the copper/molybdenum containing film is etched, the etching liquid composition of the present invention having the above-described configuration can improve etching characteristics such as etching variation, etching cone angle, and etching straightness. Therefore, when the etching liquid composition is used for the metal wiring material for electrodes of the liquid crystal display TFT, when the copper/molybdenum containing film is used, the metal wiring pattern can be formed using the etching liquid composition.

The etching method using the copper/molybdenum containing film of the upper etching liquid composition can be carried out in accordance with a usual method.

Specifically, the method includes: a step of depositing a copper/molybdenum containing film on a substrate; a step of patterning after forming a photoresist material on the copper/molybdenum containing film; and forming a patterned photoresist material using the above etching liquid composition The copper/molybdenum of the film contains a film for etching. Here, the order of lamination of the copper/molybdenum containing film formed on the substrate is not particularly limited.

Further, the above etching method further includes a step of forming a semiconductor structure between the substrate and the copper/molybdenum containing film, that is, between the substrate and the copper film or between the substrate and the molybdenum containing film. The semiconductor structure may be a semiconductor structure for a display device such as a liquid crystal display device or a plasma display panel. Specifically, the semiconductor structure is one or more films of a conductive film, an amorphous film, or a polycrystalline film, and the semiconductor structure is produced by a usual method.

The embodiments of the present invention, which are easily implemented by those skilled in the art, are described in detail. The present invention may be embodied in various forms and is not limited to the embodiments herein.

<Examples 1 to 4 and Comparative Examples 1 to 4>

The components in the following Examples 1 and the components were mixed to prepare the compositions of Examples 1 to 4 and Comparative Examples 1 to 4 of the present invention.

In the above Table 1, APS: ammonium persulfate, ATZ: 5-aminotetrazole, IDA: iminodiacetic acid, SHS: sodium hydrogen sulfate, ABF: Ammonium bifluoride, and the content of each component is in parts by weight.

<etching performance test>

In order to evaluate the effect of the etching liquid of the present invention, a copper film and a molybdenum alloy film having a thickness of 4000 Å and 300 Å were sequentially deposited on a glass substrate, and then subjected to photolithography to form a pattern to prepare a test piece.

The etching liquid compositions of Examples 1 to 4 and Comparative Examples 1 to 4 and the etching liquid compositions of Comparative Examples were carried out on a sprayable device (Mini-etcher ME-001). After the etching, etching of the etching characteristics of the copper-molybdenum alloy film was observed by a scanning electron microscope (manufactured by Hitachi, Ltd., S-4800).

According to the type of the copper/molybdenum alloy film etching solution, a 5×5 cm copper/molybdenum alloy film test piece partially over-etched on the copper/molybdenum film was etched, and the number of wiring segments was observed by a scanning electron microscope.

In order to determine the etching deviation, the measured etching time was controlled at 30% over etch.

In order to evaluate the stability, 5000 ppm of copper powder was dissolved in each etching liquid, and it was maintained at 32 degrees C for 48 hours, and the temperature change was measured.

The results are shown in Table 2.

As is apparent from the above table, the etching liquid compositions of Examples 1 to 4 and Comparative Examples 1 to 4 of the present invention were compared, and excellent results were obtained in terms of etching rate, etching deviation, wiring section, temperature rise, and the like.

In particular, Comparative Example 1 used each hydrogen peroxide as a separate oxidizing agent. In Comparative Example 2, it was found that the content of the persulfate oxidizing agent was too small to achieve the desired etching rate, and Comparative Example 3 was the persulfate oxidizing agent content. In the case of too much, Comparative Example 4 is a case where the wiring section is unsatisfactory when the hydrogen peroxide content is too large.

1 is a photograph of a cross section of a test piece observed by a scanning electron microscope after etching a copper/molybdenum film by the etching liquid composition according to Embodiment 1 of the present invention; FIG. 2 is an etching liquid combination using Comparative Example 1 of the present invention. After the copper/molybdenum film was etched, a photograph of the cross section of the test piece observed by a scanning electron microscope was used. It was found that the etching liquid composition of Comparative Example 1 could not achieve sufficient etching.

3 is a photograph of a cross section of a test piece observed by a scanning electron microscope after etching a copper/molybdenum film by the etching liquid composition of Comparative Example 3 of the present invention. As shown in Fig. 3, when the composition of Comparative Example 3 was used, the wiring segment when the etching rate was good was observed.

From the above experimental results, it is understood that the etching liquid composition of the present invention can stably carry out the etching process at a high etching rate when etching the copper/molybdenum containing film.

The features of the present invention have been described in detail above by way of embodiments, and those skilled in the art will understand that the present invention is only illustrative of the present invention, and the technology of the present invention is not limited to the embodiments. The scope of the invention is defined by the scope of the invention.

Claims (12)

An etching liquid composition containing a film of copper and molybdenum, the etching liquid composition being an etching liquid composition containing a film of copper and molybdenum containing hydrogen peroxide and persulfate as an oxidizing agent, characterized in that 100 parts by weight of hydrogen peroxide contains 0.5 to 10 parts by weight of the persulfate. . The copper and molybdenum containing film etching solution composition according to claim 1, wherein 15 to 30% by weight of hydrogen peroxide and 0.05 to 3% by weight of persulfuric acid are contained with respect to the total weight of the composition. Salt, 0.1 to 3% by weight of an etching inhibitor, 0.1 to 5% by weight of a chelating agent, 0.01 to 2% by weight of one or more compounds selected from the group consisting of inorganic acids, organic acids and salts thereof, 0.01 to 2 The wt% fluoride, and the total weight of the composition up to 100% by weight of water. The copper and molybdenum containing film etchant composition according to claim 1, wherein the persulfate is selected from the group consisting of sodium persulfate, potassium persulfate, ammonium persulfate and mixtures thereof. salt. The copper and molybdenum containing film etchant composition according to claim 1, wherein the inhibitor is selected from the group consisting of furan, thiophene, pyrrole, oxazole, imidazole, pyrazole, 1,2,4-tri Azole, tetrazole, 5-aminotetrazole, methyltetrazole, pyridazine, methylpyridazine, hydroxyethylpyridazine, pyrrolidine and alloxan, oxonium, benzothiophene, anthracene, benzo a group of imidazole, benzopyrazole, aminotetrazole, methylbenzotriazole, hydromethylbenzotriazole, hydroxymethylbenzotriazole, and mixtures thereof. The copper and molybdenum-containing etching liquid composition according to the first aspect of the invention, wherein the chelating agent is a compound containing a carboxylic acid group or a phosphoric acid group together with an amino group in the molecule. The copper and molybdenum containing film etching solution composition according to claim 1, wherein the chelating agent is selected from the group consisting of iminodiacetic acid, ammonia triacetic acid, ethylenediaminetetraacetic acid, and diethylenetriaminepentaacetic acid. Aminotrimethylenephosphonic acid, 1-hydroxyethylidene-1,1-diphosphate, ethylenediaminetetramethylenephosphoric acid, diethylenetriaminepentamethylenephosphoric acid, alanine, glutamic acid, A group of aminobutyric acid and glycine and mixtures thereof. The copper and molybdenum-containing film etching solution composition according to claim 1, wherein the additive is selected from the group consisting of inorganic acids containing sulfuric acid, nitric acid, phosphoric acid, hydrochloric acid, and hydrofluoric acid, and contains acetic acid, formic acid, and butyl. A group of acids, citric acid, glycolic acid, oxalic acid, malonic acid, valeric acid, propionic acid, tartaric acid, gluconic acid, glycine, organic acids of succinic acid, and salts thereof and mixtures thereof. The copper and molybdenum containing film etchant composition according to claim 1, wherein the etching additive is selected from the group consisting of potassium hydrogen sulfate, sodium hydrogen sulfate, sodium sulfate, potassium sulfate, ammonium sulfate, and a mixture thereof. Sulfate in the group. The patentable scope of the application as a first item and a molybdenum film containing copper etching solution composition, wherein the fluoride is dissociated F. ^- compounds ^- or ₂ HF. The copper and molybdenum containing film etchant composition according to claim 1, wherein the fluoride is selected from the group consisting of ruthenium, sodium fluoride, potassium fluoride, aluminum fluoride, borofluoric acid, ammonium fluoride. a group consisting of ammonium hydrogen fluoride, sodium hydrogen fluoride, potassium fluorohydride, ammonium fluoroborate and mixtures thereof. The copper and molybdenum-containing etching liquid composition according to the first aspect of the invention, wherein the water is deionized water having a specific resistance of 18 M?/cm or more. The copper and molybdenum-containing film-containing etching solution composition according to claim 1, further comprising an additive selected from the group consisting of a hydrogen peroxide stabilizer, an etching stabilizer, a glass etching inhibitor, and a mixture thereof. group.