TW201514278A - 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, control side etching of a molybdenum or molybdenum alloy film, realize a stable etching process, improve etching properties of etching coning angle, etching deviation, and etching linearity. The etchant composition comprises, relative to the total weight, a hydrogen peroxide content of 10 to 30 wt%, an etching inhibitor content of 0.1 to 5 wt%, a chelating agent content of 0.1 to 5 wt%, an etching additive content of 0.1 to 5 wt%, a fluoride content of 0.01 to 2 wt%, a side etching inhibitor content of 0.01 to 2 wt%, and water as the remainder making the total amount as 100 wt%.

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.

When the thin film metal is molybdenum or molybdenum alloy, the etching speed is faster than the etching speed of copper. In the etching process, on the boundary of copper, molybdenum or molybdenum alloy film, molybdenum or molybdenum alloy is over-etched to cause side etching. The phenomenon. Especially for alloys with a high molybdenum content, the etching speed is very fast and the side etching phenomenon is serious. This phenomenon can be controlled when a side etching inhibitor is added.

In the case of simultaneously etching a copper film and a molybdenum-containing film, the related art as an etchant composition that can be used is disclosed in Korean Patent Laid-Open Publication No. 2006-0064881, Patent Publication No. An etching solution of a copper/molybdenum containing film based on hydrogen peroxide is disclosed in No. 2006-0099089. 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 solution for controlling the side etching of a molybdenum or molybdenum alloy film when etching a copper and molybdenum containing film, achieving stable etching engineering, and improving etching characteristics such as etching cone angle, etching deviation, and etching straightness. combination.

The copper and molybdenum film-containing etchant composition according to an embodiment of the present invention contains 10 to 30% by weight of hydrogen peroxide with respect to the total weight of the composition; and 0.1 to 5% by weight of an etching inhibitor selected from the group consisting of a monocyclic heterocyclic compound containing at least one or more heteroatoms of oxygen, sulfur and nitrogen, a group consisting of the monocyclic heterocyclic ring and a benzene ring condensed structure of a complex ring compound and a mixture thereof; Up to 5% by weight of a chelating agent; containing 0.1 to 5% by weight of an etching additive which is one or more compounds selected from the group consisting of inorganic acids, organic acids and salts thereof; containing 0.01 to 2% by weight of fluoride; containing 0.01 to 2% by weight of a side etching inhibitor comprising a compound having one or more active groups in a group consisting of an amino group, a hydroxyl group, a carbonyl group and a methyl group in a condensation structure of pyrimidine and imidazole; and bringing the total weight of the composition to 100 % by weight of water.

In the above etchant composition, the inhibitor is selected from the group consisting of furan, thiophene, pyrrole, oxazole, imidazole, pyrazole, 1,2,4-triazole, tetrazole, 5-aminotetrazole, methyl Tetrazole, pyridazine, methylpyrazine, hydroxyethylpyridazine, pyrrolidine and alloxan, oxonium, benzothiophene, anthracene, benzimidazole, benzopyrazole, aminotetrazole, methylbenzene A group of triazoles, hydromethylbenzotriazoles, hydroxymethylbenzotriazoles, 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.

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, and B. A group consisting of diamine tetramethylphosphoric acid, diethylene triamine penta methylene phosphate, 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 potassium sulfate, sodium hydrogen sulfate, sodium sulfate, sodium persulfate, potassium sulfate, potassium persulfate, ammonium sulfate, ammonium persulfate, and mixtures thereof.

The fluoride is dissociated F. ^- compounds ^- 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 scoliosis inhibitor is a purine base selected from the group consisting of adenine, guanine, hypoxanthine, xanthine, cocaine, caffeine, isoguanine, uric acid, and mixtures thereof.

The etch inhibitors are adenine, guanine, isoguanine, 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 electrode of the TFT-LCD display is etched according to the etching liquid composition of the invention, the side etching of the molybdenum containing film can be controlled, thereby realizing a stable etching process, thereby Etching characteristics such as etching cone angle, etching deviation, and etching straightness are improved.

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 an etching liquid composition according to Embodiment 1 of the present invention, after etching a copper/molybdenum film, using a tilt A photograph of a cross section of a test piece observed by a scanning electron microscope; and FIG. 4 is a photograph of a cross section of a test piece observed by a tilt scanning electron microscope after etching the copper/molybdenum film by the etching liquid composition of Comparative Example 3 of the present invention.

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.

The copper and molybdenum film-containing etchant composition according to an embodiment of the present invention contains 10 to 30% by weight of hydrogen peroxide with respect to the total weight of the composition; and 0.1 to 5% by weight of an etching inhibitor selected from the group consisting of a monocyclic heterocyclic compound containing at least one or more heteroatoms of oxygen, sulfur and nitrogen, a group consisting of the monocyclic heterocyclic ring and a benzene ring condensed structure of a complex ring compound and a mixture thereof; Up to 5% by weight of a chelating agent; containing 0.1 to 5% by weight of an etching additive, which is one or more compounds selected from the group consisting of inorganic acids, organic acids and salts thereof Containing 0.01 to 2% by weight of fluoride; containing 0.01 to 2% by weight of a side etching inhibitor comprising a group consisting of an amino group, a hydroxyl group, a carbonyl group and a methyl group in a condensation structure of pyrimidine and imidazole; More than one active group of compounds; and water having a total weight of the composition of up to 100% by weight.

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 copper and molybdenum containing film-containing etching solution composition according to an embodiment of the present invention contains a) 10 to 30% by weight of hydrogen peroxide with respect to the total weight of the composition; and b) 0.1 to 5% by weight of an etching inhibitor Containing c) 0.1 to 5% by weight of a chelating agent; d) 0.1 to 5% by weight of an etching additive; e) 0.01 to 2% by weight of fluoride; f) 0.01 to 2% by weight of a side etching inhibitor And g) water having a total weight of the composition of up to 100% by weight.

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 10% 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 15 to 25% by weight.

b) 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 0.1 to 5% by weight, preferably 0.1 to 2% by weight based on the total weight of the etching liquid 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 5% by weight, the etching rate is slowed and the efficiency is inefficient.

c) 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.

d) etching additive

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 used alone or in combination of two or more.

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 may be potassium hydrogen sulfate, sodium hydrogen sulfate, sodium sulfate, sodium persulfate, potassium sulfate, potassium persulfate, ammonium sulfate, ammonium persulfate.

Among them, potassium hydrogen sulfate which is effective for improving etching characteristics is preferable.

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.

e) 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 present invention is a fluoride dissociates F ^- compound or HF2- ions may be hafnium, sodium fluoride, potassium fluoride, aluminum fluoride, boron hydrofluoric acid, ammonium fluoride, ammonium bifluoride, sodium bifluoride, potassium bifluoride 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.

f) side erosion inhibitor

In the simultaneous etching of the copper/molybdenum containing film, in order to control the side etching of the molybdenum or molybdenum alloy film, the content of the fluoride in the etching liquid composition is generally reduced, or the content of the etching inhibitor is increased. However, when the content of the fluoride is low, a residue of molybdenum or a molybdenum alloy occurs. When the etching inhibitor is added, the etching speed of copper is remarkably lowered, and etching work is difficult. On the other hand, the use of the side etching inhibitor of cerium or its inducer prevents the occurrence of molybdenum or molybdenum alloy film residue and the slowing of the copper etching rate.

The above-mentioned side etching inhibitor includes a compound having one or more active groups in a group consisting of an amino group, a hydroxyl group, a carbonyl group and a methyl group in a condensation structure of pyrimidine and imidazole; since it is included in a condensation structure of pyrimidine and imidazole, A compound having one or more groups of an amino group, a hydroxyl group, a carbonyl group, and a methyl group has excellent adsorption characteristics for molybdenum or a molybdenum alloy, and has a significant effect of suppressing side etching, and can effectively improve etching characteristics.

Specifically, the above-mentioned side inhibitor is a purine base selected from the group consisting of adenine, guanine, hypoxanthine, xanthine, cocaine, caffeine, isoguanine, uric acid, and mixtures thereof. The lateral erosion inhibitors can also be adenine, guanine, isoguanine, and mixtures thereof.

The content of the undercut inhibitor is from 0.01 to 2% by weight, preferably from 0.05 to 2% by weight, based on the total weight of the composition. When the weight is less than 0.01% by weight, the effect of suppression is small; when it exceeds 2% by weight, the etching rate of the molybdenum or molybdenum alloy is remarkably slow, and it is difficult to perform etching work.

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 can be a hydrogen peroxide additive, Etching stabilizer, glass etching inhibitor, and 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.

The etching liquid composition of the present invention having the above-described configuration can prevent the occurrence of side etching of the molybdenum-containing film when etching the copper/molybdenum-containing film, realize stable etching, and can improve etching deviation, etching cone angle, etching straightness, and the like. Etching characteristics. 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 6 and Comparative Examples 1 to 3>

The components in the following Examples 1 and the components were mixed to prepare the compositions of Examples 1 to 6 and Comparative Examples 1 to 3 of the present invention.

In the above Table 1, ATZ: 5-aminotetrazole, IDA: iminodiacetic acid, and PHS: Potassium hydrogen sulfate, the content of each component is in parts by weight. .

<Test Example: 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 5000 Å were deposited on a glass substrate, respectively, and then subjected to photolithography to form a pattern to prepare a test piece. The etchant composition of Examples 1 to 6 and Comparative Examples 1 to 3 and the etchant composition of the comparative example were sprayable Etching was performed on the device (Mini-etcher ME-001) and maintained at 32 degrees Celsius for 120 seconds.

After the etching, the etching end point is measured, and the etching characteristics of the copper-molybdenum alloy film can be etched by a scanning electron microscope (manufactured by Hitachi, Ltd., S-4800) for whether or not an etching deviation, an etching taper angle, or a side etching of the molybdenum alloy film occurs. Observe. The results are shown in Table 2.

As shown in Table 2, the etching liquid compositions of Examples 1 to 6 and Comparative Examples 1 to 3 of the present invention were compared, and it was found that they had good results in etching cone angle, etching deviation, and etching straightness.

Further, in order to observe whether or not there was side etching, the cross section of the etched copper/molybdenum containing film was observed using a scanning electron microscope using the etching liquid compositions of Example 1 and Comparative Example 1, and the results are shown in FIGS. 1 and 2 . Shown.

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.

As shown in Fig. 1, as a result of etching by the etching liquid composition of Example 1, no molybdenum side etching was observed. However, the etching liquid composition of Comparative Example 1 was used, as shown in FIG. 2, In the lower part of the copper film, molybdenum sinks inward and severe side etching occurs.

Further, in order to confirm whether or not molybdenum residue was generated, the etching liquid compositions of Example 1 and Comparative Example 3 were used, and after etching the copper/molybdenum film, the cross section of the test piece was observed using a tilt scanning electron microscope, and the results are shown in Fig. 3 and Fig. 3, respectively. 4 is shown.

3 is a photograph of a cross section of a test piece observed by a tilt scanning electron microscope after etching a copper/molybdenum film by the etching liquid composition according to Embodiment 1 of the present invention; and FIG. 4 is an etching liquid using Comparative Example 3 of the present invention. The composition was subjected to etching of a copper/molybdenum film, and a photograph of a cross section of the test piece observed using a tilt scanning electron microscope was used.

As shown in FIG. 3, when the etching liquid composition of Example 1 was used, no molybdenum residue appeared, and when the etching liquid composition of Comparative Example 3 was used, a molybdenum residue was observed as shown in FIG.

According to the above test results, when the copper/molybdenum containing film is simultaneously etched by the etching liquid composition of the present invention, side etching of the molybdenum containing film can be suppressed, stable etching can be realized, and etching taper, etching deviation, and etching can be improved. Etching characteristics such as straightness.

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)

A copper and molybdenum containing film etchant composition characterized by containing 10 to 30% by weight of hydrogen peroxide relative to the total weight of the composition; and containing 0.1 to 5% by weight of an etching inhibitor selected from the group consisting of a monocyclic heterocyclic compound containing at least one or more of oxygen, sulfur and nitrogen, a group consisting of the monocyclic heterocyclic ring and a benzene ring condensed structure, and a mixture thereof; 5 wt% of a chelating agent; containing 0.1 to 5% by weight of an etching additive, which is one or more compounds selected from the group consisting of inorganic acids, organic acids and salts thereof; containing 0.01 to 2% by weight of fluoride; containing 0.01 to 2 a % by weight of a side etching inhibitor comprising a compound having one or more active groups in a group consisting of an amino group, a hydroxyl group, a carbonyl group and a methyl group in a condensation structure of pyrimidine and imidazole; and a total weight of the composition of up to 100% by weight % water. 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. Acid, citric acid, glycolic acid, oxalic acid, malonic acid, valeric acid, propionic acid, wine A group of organic acids of lithic acid, gluconic acid, glycine, 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, sodium persulfate, potassium sulfate, potassium persulfate. a sulfate in a group of ammonium sulfate, ammonium persulfate, and mixtures thereof. 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 ^- or HF2 ^- compound. 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 film etching solution composition according to claim 1, wherein the side etching inhibitor is selected from the group consisting of adenine, guanine, hypoxanthine, scutellaria, cocaine, and coffee. The purines in the group consisting of, guanine, uric acid and mixtures thereof. The copper and molybdenum-containing film etching solution composition according to claim 1, wherein the side etching inhibitor is adenine, guanine, isoguanine, and a mixture thereof. The copper and molybdenum-containing etching liquid composition according to claim 1, wherein the water is deionized water having a specific resistance of 18 MΩ/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.