KR20150039526A - Etching composition for copper and molibdenum containing film - Google Patents

Abstract

The present invention relates to an etching composition to enable a stable etching process by preventing an undercut on molybdenum or a molybdenum containing film in the etching process of a copper and molybdenum containing film, thereby improving etching properties on tapering angles, CD loss, and etching linearity. The etching composition is composed of 10-30 wt% of hydrogen peroxide, 0.1-5 wt% of an etching inhibitor, 0.1-5 wt% of a chelating agent, 0.1-5 wt% of an etching additive, 0.01-2 wt% of a fluorine compound, 0.01-2 wt% of an undercut inhibitor, and remaining amount of water based on the total weight of the composition.

Description

[0001] ETCHING COMPOSITION FOR COPPER AND MOLIBDENUM CONTAINING FILM [0002]

The present invention relates to an etchant composition of a copper and molybdenum or molybdenum alloy film (hereinafter simply referred to as a copper / molybdenum-containing film), particularly to an etchant composition of a copper and molybdenum containing film used as an electrode of a TFT-LCD display.

A semiconductor device and a fine circuit such as a TFT-LCD are formed by uniformly applying a photoresist to a conductive metal film such as aluminum, an aluminum alloy, a copper and a copper alloy formed on a substrate, an insulating film such as a silicon oxide film or a silicon nitride film, After a light is irradiated through an engraved mask, a photoresist of a desired pattern is formed through development, a pattern is transferred to a metal film or an insulating film under the photoresist by dry or wet etching, and then unnecessary photoresist is removed by a peeling process Lt; RTI ID = 0.0 > lithography < / RTI >

Gate and data metallization of large displays use copper metal with lower resistance and environmental friendliness than conventional aluminum and chromium wiring. However, copper has a low adhesion to glass substrate and silicon insulating film and diffuses into silicon film, and titanium, molybdenum and the like are used as the lower barrier metal.

When the barrier metal is a molybdenum or molybdenum alloy, the etch rate of the molybdenum or molybdenum alloy film is very high compared to the etching rate of copper, so that the undercut phenomenon of the molybdenum or molybdenum alloy film at the copper and molybdenum or molybdenum alloy film boundary is excessive during the etching process Can occur. In particular, when an alloy having a high molybdenum content is used, the etch rate is very large and the undercut phenomenon is intensified. This phenomenon can be controlled by adding an undercut inhibitor.

Korean Patent Laid-Open Publication Nos. 2006-0064881 and 2006-0099089 disclose etchants for copper / molybdenum-containing films based on hydrogen peroxide, which are related to etchant compositions that can be used in simultaneous etching of copper films and molybdenum containing films have. However, as the etchant is repeatedly etched and the metal content of the etchant increases, the etch characteristics such as the taper angle, the sidewall, and the straightness of the etch are lost, and the metal content of the etchant is low, .

Patent Publication No. 2006-0064881 (published on June 14, 2006) Patent Publication No. 2006-0099089 (published on September 19, 2006)

It is an object of the present invention to provide an etchant composition capable of improving etching properties such as taper angle, sidewall and visual straightness by controlling the undercut of molybdenum or molybdenum alloy film during etching of the copper / molybdenum containing film, .

The etchant composition of the copper / molybdenum containing film according to one aspect of the present invention comprises 10 to 30% by weight hydrogen peroxide, based on the total weight of the composition; A monocyclic heterocyclic compound containing at least one hetero atom selected from oxygen, sulfur, and nitrogen in the molecule, a heterocyclic compound having a condensed structure of the above-mentioned monocyclic heterocycle and a benzene ring, and a mixture thereof 0.1 to 5 wt% of an etch inhibitor selected; 0.1 to 5% by weight of a chelating agent; 0.1 to 5% by weight of an etching additive comprising at least one compound selected from the group consisting of inorganic acids, organic acids and salts thereof; 0.01 to 2% by weight of a fluorine compound; 0.01 to 2% by weight of an undercut inhibitor comprising a compound having at least one functional group in the group consisting of an amino group, a hydroxyl group, a carbonyl group and a methyl group in a condensed structure of pyrimidine and imidazole; And water so that the total weight of the composition is 100% by weight.

In the above etching composition, the etching inhibitor may be at least one selected from the group consisting of furane, thiophene, pyrrole, oxazole, imidazole, pyrazole, triazole, Tetrazole, 5-aminotetrazole, methyltetrazole, piperazine, methylpiperazine, hydroxyethylpiperazine, pyrrolidine, and the like. a compound selected from the group consisting of pyrrolidine, alloxan, benzofurane, benzothiophene, indole, benzimidazole, benzpyrazole, tolutriazole, Hydrotoluenesulfonic acid, hydrotolutriazole, hydroxytolutriazole, and mixtures thereof.

The chelating agent may be a compound containing a carboxylic acid group or a phosphonic acid group together with an amino group in a molecule.

The chelating agent may be at least one selected from the group consisting of iminodiacetic acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetrinitrilacetic acid, aminotris (methylenephosphonic acid) aminotris (methylenephosphonic acid)), (1- hydroxy-ethane-1,1-diyl) bis (phosphonic acid) ((1- hydroxyethane - 1, 1- diyl) bis (phosphonic acid ethylenediamine tetra (methylene phosphonic acid), diethylenetriamine penta (methylene phosphonic acid), alanine (alanine), glutamic acid (glutamic acid) ), Aminobutyric acid, glycin, and mixtures thereof.

Wherein the etch additive is selected from the group consisting of inorganic acids including sulfuric acid, nitric acid, and phosphoric acid; Organic acids including acetic acid, formic acid, butanoic acid, citric acid, glycolic acid, oxalic acid, malonic acid, pentanoic acid, propionic acid, tartaric acid, gluconic acid, glycosic acid and succinic acid; Salts thereof; And a mixture thereof.

The etching additive may be selected from the group consisting of potassium hydrogen sulfate, sodium hydrogen sulfate, sodium sulfate, sodium persulfate, potassium sulfate, potassium persulfate ), Ammonium sulfate, ammonium persulfate, and mixtures thereof.

The fluorine compound may be a compound dissociated to generate F ^- or HF ₂ ^- .

The fluorine compound may be selected from the group consisting of HF, NaF, KF, AlF ₃ , HBF ₄ , NH ₄ F, NH ₄ HF ₂ , NaHF ₂ , KHF ₂ , NH ₄ BF _4, .

Wherein the undercut inhibitor is selected from the group consisting of adenine, guanine, hypoxanthine, xanthine, theobromine, caffeine, isoguanine, uric acid, And a mixture thereof.

In addition, the undercut inhibitor may be selected from the group consisting of adenine, guanine, isoguanine, and mixtures thereof.

The water may be deionized water having a resistivity value of 18 M? / Cm or more.

The etchant composition may further comprise additives selected from the group consisting of a hydrous stabilizer, an etching stabilizer, a glass etch inhibitor, and mixtures thereof.

Other details of the embodiments of the present invention are included in the following detailed description.

The etchant composition according to the present invention controls the occurrence of undercut of the molybdenum-containing film during etching of the copper / molybdenum-containing film used as a TFT-LCD display electrode, thereby enabling a stable etching process. As a result, The etching characteristics can be improved.

FIG. 1 is a photograph of a cross section of a specimen after etching a copper / molybdenum film using an etching solution composition according to Example 1 with a scanning electron microscope. FIG.
FIG. 2 is a photograph of a cross section of a specimen after etching a copper / molybdenum film using an etching solution composition according to Comparative Example 1 with a scanning electron microscope. FIG.
FIG. 3 is a photograph of a specimen obtained by etching a copper / molybdenum film using an etching solution composition according to Example 1 by using a tilted scanning electron microscope. FIG.
FIG. 4 is a photograph of a specimen obtained by etching a copper / molybdenum film with a tilted scanning electron microscope using the etching solution composition according to Comparative Example 3. FIG.

BRIEF DESCRIPTION OF THE DRAWINGS The present invention is capable of various modifications and various embodiments, and specific embodiments are illustrated in the drawings and described in detail in the detailed description. It is to be understood, however, that the invention is not to be limited to the specific embodiments, but includes all modifications, equivalents, and alternatives falling within the spirit and scope of the invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.

The present invention provides a composition comprising 10 to 30% by weight hydrogen peroxide, based on the total weight of the composition; A monocyclic heterocyclic compound containing at least one hetero atom selected from oxygen, sulfur, and nitrogen in the molecule, a heterocyclic compound having a condensed structure of the above-mentioned monocyclic heterocycle and a benzene ring, and a mixture thereof 0.1 to 5 wt% of an etch inhibitor selected; 0.1 to 5% by weight of a chelating agent; 0.1 to 5% by weight of an etching additive comprising at least one compound selected from the group consisting of inorganic acids, organic acids and salts thereof; 0.01 to 2% by weight of a fluorine compound; 0.01 to 2% by weight of an undercut inhibitor comprising a compound having at least one functional group in the group consisting of an amino group, a hydroxyl group, a carbonyl group and a methyl group in a condensed structure of pyrimidine and imidazole; And water so that the total weight of the composition is 100% by weight based on the total weight of the copper / molybdenum-containing film.

Hereinafter, the etchant composition of a copper / molybdenum-containing film according to an embodiment of the present invention will be described in more detail.

The etchant composition of the present invention can simultaneously etch the copper / molybdenum containing film. Here, the term "copper / molybdenum-containing film" refers to a copper film and a molybdenum film, or a copper film and a molybdenum alloy film. The molybdenum alloy is an alloy of molybdenum and various metals, preferably titanium, tantalum, chromium, neodymium, Indium or tin, and most preferably an alloy with titanium.

B) 0.1 to 5% by weight of an etch inhibitor, c) 0.1 to 5% by weight of a chelating agent, d) 0.1 to 5% by weight of an etching additive, based on the total weight of the composition, Molybdenum-containing film comprising water, wherein the total weight of the composition is from 0.01 to 2 wt%, e) 0.01 to 2 wt% of a fluorine compound, f) 0.01 to 2 wt% of an undercut inhibitor, and g) .

Hereinafter, each component of the etchant composition of the copper / molybdenum-containing film according to one embodiment of the present invention will be described in more detail.

a) Hydrogen peroxide

In the etchant composition of the present invention, hydrogen peroxide acts as a main oxidizing agent for copper and a molybdenum or molybdenum alloy.

The hydrogen peroxide may be contained in an amount of 10 to 30% by weight based on the total weight of the etchant composition. If hydrogen peroxide is contained in an amount of less than 10% by weight, the oxidizing power of the copper and molybdenum alloy may not be sufficient, and etching may not be performed. If the hydrogen peroxide is contained in excess of 30% by weight, the etching speed becomes too fast. It may be preferable to include 15 to 25% by weight from the viewpoint of achieving an appropriate etching rate, preventing etch residue and etch failure, reducing CD loss and facilitating process control.

b) Etch inhibitor

In the etchant composition of the present invention, the etch inhibitor reduces the CD loss of the pattern by controlling the etch rate of the copper, molybdenum or molybdenum alloy, increases the process margin, and provides the etch profile with appropriate taper angles.

Specifically, the etching inhibitor is a monocyclic heterocyclic compound containing at least one heteroatom selected from oxygen, sulfur and nitrogen in the molecule, or a heterocyclic compound having a condensed structure of the monocyclic heterocycle and the benzene ring Lt; / RTI > The monocyclic heterocyclic compound may be a heterocyclic aromatic compound or a heterocyclic aliphatic compound having a monocyclic structure having 1 to 10 carbon atoms. Specific examples thereof include furan, thiophene, pyrrole, Such as oxazole, imidazole, pyrazole, triazole, tetrazole, 5-aminotetrazole, or methyltetrazole, and the like. A heterocyclic aromatic compound; But are not limited to, heterocyclic aliphatic compounds such as piperazine, methylpiperazine, hydroxyethylpiperazine, pyrrolidine, and alloxan. no. The heterocyclic compound having a condensation structure of benzene with a monocyclic hetero ring containing at least one hetero atom selected from oxygen, sulfur and nitrogen in the molecule may be benzofurane, benzothiophene, Indole, benzimidazole, benzpyrazole, tolutriazole, hydrotolutriazole, or hydroxytolutriazole, and the like can be mentioned. However, , But are not limited thereto. These compounds may be used singly or in combination of two or more.

The etching inhibitor may be 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 etchant composition. When the etching inhibitor is contained in an amount of less than 0.1% by weight, the etching rate is difficult to control, the ability to control the taper angle is reduced, and the process margin is low, There is a problem of inefficiency due to a decrease in speed.

c) Chelating agent

In the etchant composition of the present invention, the chelating agent forms a chelate with metal ions such as copper ions, molybdenum, or alloy ions thereof generated during the etching process, thereby inactivating the chelating agent, thereby preventing occurrence of side reactions by these metal ions, So that the etching characteristics can be maintained. Particularly, in the case of a copper layer, if a large amount of copper ions remain in the etching solution composition, there is a problem that a passivation film is formed and oxidized and not etched. However, formation of a passivation film of copper ion can be prevented when the chelating agent is added. In addition, the chelating agent can prevent the decomposition reaction of hydrogen peroxide itself and increase the stability of the etching solution. Therefore, if no chelating agent is added to the etching solution composition, the oxidized metal ions are activated during the etching process, the etching characteristics of the etching solution are easily changed, and the decomposition reaction of hydrogen peroxide is promoted, so that heat generation and explosion may occur.

The chelating agent may be a compound containing a carboxylic acid group or a phosphonic acid group together with an amino group in a molecule. Specific examples include iminodiacetic acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetrinitrilacetic acid, aminotris (methylenephosphonic acid), aminotris (methylenephosphonic acid) acid)), (1- hydroxy-ethane-1,1-diyl) bis (phosphonic acid) ((1- hydroxyethane - 1, 1- diyl) bis (phosphonic acid ethylenediamine tetra (methylene phosphonic acid), diethylenetriamine penta (methylene phosphonic acid), alanine (alanine), glutamic acid (glutamic acid) Aminobutyric acid, or glycin. One of these may be used alone, or a mixture of two or more thereof may be used.

The chelating agent may be contained in an amount of 0.1 to 5% by weight, preferably 0.1 to 3% by weight based on the total weight of the etchant composition. When the chelating agent is contained in an amount of less than 0.1 wt%, the amount of the metal ion that can be deactivated is too small to have an ability to control the hydrogen peroxide decomposition reaction. When the chelating agent is contained in an amount exceeding 5 wt%, the chelating agent can not be expected to deactivate the metal. There is a problem.

d) etching additive

The etch additive serves as a co-oxidant for copper and molybdenum or molybdenum alloys and improves the taper profile. As the etching additive, an inorganic acid, an organic acid, or a salt thereof may be used, and either one of them or a mixture of two or more thereof may be used.

The inorganic acid may be sulfuric acid, nitric acid or phosphoric acid. The organic acid may be acetic acid, formic acid, butanoic acid, citric acid, glycolic acid, oxalic acid, malonic acid, pentanoic acid, propionic acid, tartaric acid, gluconic acid, . In addition, the salt may be selected from the group consisting of potassium hydrogen sulfate, sodium hydrogen sulfate, sodium sulfate, sodium persulfate, potassium sulfate, potassium persulfate, It may be a sulfate such as ammonium sulfate or ammonium persulfate.

Of these, sulfates such as potassium hydrogensulfate, which are more effective in improving etching properties, may be preferred.

The etching additive may be contained in an amount of 0.1 to 5% by weight, preferably 0.1 to 3% by weight based on the total weight of the etchant composition. When the etching additive is contained in an amount of less than 0.1% by weight, the effect of improving the taper profile by the use of the etching additive is insignificant. If the etching additive is contained in an amount exceeding 5% by weight, the etching property may be deteriorated due to an excessive amount of the etching additive.

e) fluorine compound

In the etchant composition of the present invention, the fluorine compound improves the etching rate of the molybdenum-containing film when the copper / molybdenum-containing film is etched at the same time, thereby reducing the tail length and removing the residue of the molybdenum or molybdenum alloy, . Increasing the tail of the molybdenum or molybdenum alloy may reduce the brightness and it should be removed as residues remain on the substrate and underlying film as they reduce electrical shorts, poor wiring and brightness.

As the fluorine compound, a compound capable of being dissociated to generate F ^- or HF ₂ ^- can be used. Specific examples thereof include HF, NaF, KF, AlF ₃ , HBF ₄ , NH ₄ F, NH ₄ HF ₂ , NaHF ₂ , KHF ₂ and NH ₄ BF ₄ . Mixtures may be used.

The fluorine compound may be contained in an amount of 0.01 to 2% by weight, preferably 0.01 to 1% by weight based on the total weight of the etchant composition. If the fluorine compound is contained in an amount less than 0.01% by weight, the residue of the molybdenum or molybdenum alloy can not be effectively removed. If the fluorine compound is contained in an amount exceeding 2% by weight, the lower film such as a glass substrate can be etched.

f) Undercut inhibitor

In order to control the undercut of the molybdenum or molybdenum alloy film during co-etching of the copper / molybdenum containing film, the content of the fluorine compound in the etching solution composition is usually decreased or the etching inhibitor content is increased. However, when the content of the fluorine compound is decreased, residues of the molybdenum or molybdenum alloy may be generated. If the content of the etching inhibitor is increased, the etching rate of the copper is remarkably decreased and it is difficult to carry out the etching process. On the contrary, by applying the undercut inhibitor of purine or its derivative, it is possible to prevent the residue of the molybdenum or molybdenum alloy film from being generated and the etching rate of copper to be lowered.

The undercut inhibitor may be a compound containing at least one functional group in the group consisting of an amino group, a hydroxyl group, a carbonyl group and a methyl group in a condensed structure of pyrimidine and imidazole. As described above, by containing at least one functional group in the group consisting of an amino group, a hydroxy group, a carbonyl group, and a methyl group in the condensed structure of pyrimidine and imidazole, the excellent adsorption property to molybdenum and molybdenum alloy is exhibited, It is possible to exhibit a better etching property improving effect.

Specific examples thereof include adenine, guanine, hypoxanthine, xanthine, theobromine, caffeine, isoguanine, uric acid, etc. Of the purine base, among which adenine, guanine, and isoguanine may be preferred.

The undercut inhibitor may be included in an amount of 0.01 to 2% by weight, preferably 0.05 to 2% by weight based on the total weight of the composition. If the undercut inhibitor is contained in an amount less than 0.01% by weight, the effect of using the undercut inhibitor is insignificant. If the undercut inhibitor is used in an amount exceeding 2% by weight, the etching rate of the molybdenum or molybdenum alloy is remarkably decreased.

g) water

In the etchant composition of the present invention, water is not particularly limited, but deionized water may be preferable, and deionized water having a specific resistance value of 18 M OMEGA. / Cm or more, which is a degree at which ions are removed in water, may be more preferable.

The water may be included in an amount such that the total weight of the etchant composition is 100% by weight.

h) Other additives

The etchant composition of the copper / molybdenum containing film of the present invention may further comprise any additive commonly used in the etchant composition to improve etch performance. Examples of the additive include a hydrous stabilizer, an etching stabilizer, and a glass etching inhibitor. These may be used singly or in combination of two or more.

The hydrothermal stabilizer acts to control the hydrogen peroxide decomposition reaction when the metal ion content in the etching solution is high by repeating the etching process. Specifically, phosphate, glycol, amines, or a mixture thereof may be used as the above-mentioned water-soluble stabilizer.

When the hydrothermal stabilizer is included in the etchant composition, it may be contained in an amount of 0.1 to 5% by weight, preferably 0.5 to 3% by weight based on the total weight of the composition. When the hydrous stabilizer is contained in an amount of less than 0.1% by weight, the control effect on the hydrogen peroxide decomposition reaction is insignificant, and if it is contained in an amount exceeding 5% by weight, the etching performance may be lowered.

The etchant composition of the present invention having the above composition enables a stable etching process by controlling the occurrence of undercut of the molybdenum-containing film when the copper / molybdenum-containing film is etched. As a result, the etching characteristics such as taper angle, seed loss, and visual straightness can be improved. Accordingly, the etchant composition is useful as an etchant composition for forming a metal wiring pattern when a copper / molybdenum-containing film is used as a metal wiring material for a gate, a source, or a drain electrode constituting a TFT (Thin Film Transistor) of a liquid crystal display Can be used.

The etching method of the copper / molybdenum-containing film using the above-mentioned etchant composition can be carried out by a conventional method.

Depositing a copper / molybdenum containing film on the substrate; Forming a photoresist film on the copper / molybdenum-containing film and patterning the film; And etching the copper / molybdenum-containing film on which the patterned photoresist film is formed by using the etching liquid composition described above. In this case, the copper / molybdenum- / Molybdenum-containing film is not particularly limited.

In addition, the etching method may include 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, a plasma display panel, or the like. Specifically, the semiconductor structure may include one or more layers selected from a dielectric film, a conductive film, and a silicon film such as amorphous or polycrystalline, and these semiconductor structures may be manufactured by a conventional method.

Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily carry out the present invention. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.

< Example  1 to 6 and Comparative Example  1 to 3>

The compositions of Examples 1 to 6 and Comparative Examples 1 to 3 according to the present invention were prepared by mixing each component with the ingredient contents shown in Table 1 below.

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2 Comparative Example 3 Hydrogen peroxide 20 20 20 20 20 20 20 20 20 Etching
Inhibitor ATZ 1.0 1.0 1.0 1.0 1.0 1.0 1.0 2.5 1.0 Chelating agent IDA 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Etching
additive PHS 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Fluorine
compound NH ₄ HF ₂ 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.01 Undercut inhibitor Guanine 0.1 0.2 0.5 - - - - - - Adenine - - - 0.1 0.2 0.5 - - - water 75.9 75.8 75.5 75.9 75.8 75.5 76.0 73.0 75.99

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

< Test Example : Etching  Performance evaluation>

A 5500 Å thick copper film and a molybdenum film were successively deposited on a glass substrate to prepare a test piece. A resist film patterned by the photolithography process was formed on the specimen, and etching of the copper / molybdenum film was performed using the etchant compositions of Examples 1 to 6 and Comparative Examples 1 to 3, respectively. At this time, the etching process was performed at 32 DEG C for 120 seconds using a sprayable apparatus (Mini-etcher ME-001).

The etch end point was measured after completion of etching. Etching characteristics of etched copper / molybdenum films such as CD loss, taper angles, and occurrence of undercuts of molybdenum films were observed using a scanning electron microscope (Hitachi, S-4800), and the presence or absence of molybdenum residues And confirmed by using a tilt scanning electron microscope. The results are shown in Table 2 below.

Etch end point
[second] CD loss
[Mu m] Taper angle (°) Residue of molybdenum film Undercut of molybdenum membrane Example 1 70 0.91 48.1 none none Example 2 75 0.90 47.5 none none Example 3 80 0.85 48.2 none none Example 4 80 0.89 46.2 none none Example 5 82 0.85 45.2 none none Example 6 85 0.84 45.1 none none Comparative Example 1 70 0.99 55.6 none has exist Comparative Example 2 200 120 sec unetched Comparative Example 3 100 0.76 51.9 has exist none

As shown in Table 2, the etchant compositions of Examples 1 to 6 according to the present invention had excellent results in terms of etch bias, seed loss, taper angle, and tail length as compared with the etchant compositions of Comparative Examples 1 to 3 Respectively.

In order to observe whether or not the undercut occurred, the specimen of the copper / molybdenum film etched using the etching composition of Example 1 and Comparative Example 1 was observed with a scanning electron microscope. The results are shown in Figs. 1 and 2. Fig.

FIG. 1 is a photograph of a piece of a specimen after etching a copper / molybdenum film using a etchant composition according to Example 1 by a scanning electron microscope, and FIG. 2 is a photograph of a copper / A photograph of the cross section of the specimen after etching the molybdenum film with a scanning electron microscope.

As shown in Fig. 1, when the etching composition of Example 1 was used, no molybdenum undercut was observed. However, when the etchant composition of Comparative Example 1 was used, as shown in FIG. 2, the molybdenum film was poured inward from the bottom of the copper film and it was confirmed that the undercut was severely generated.

In order to confirm whether or not the molybdenum residue was generated, copper / molybdenum films were etched using the etching composition according to Example 1 and Comparative Example 3, and the pieces of the specimen were tilted and confirmed by scanning electron microscope image. The results are shown in Figs. 3 and 4, respectively.

FIG. 3 is a photograph of a specimen obtained by etching with a copper / molybdenum film by a scanning electron microscope using the etchant composition according to Example 1. FIG. 4 is a graph showing a copper / molybdenum film And the specimen was observed with a scanning electron microscope after tilted.

As shown in FIG. 3, when the etchant composition of Example 1 was used, no molybdenum residue was observed, but when the etchant composition of Comparative Example 1 was used, molybdenum residue was observed as shown in FIG.

From the above experimental results, it can be seen that the etchant composition according to the present invention controls the occurrence of undercut of the molybdenum-containing film during etching of the copper / molybdenum-containing film, thereby enabling a stable etching process. As a result, It can be confirmed that the etching characteristics are improved.

While the present invention has been particularly shown and described with reference to specific embodiments thereof, those skilled in the art will appreciate that such specific embodiments are merely preferred embodiments and that the scope of the present invention is not limited thereby. something to do. It is therefore intended that the scope of the invention be defined by the claims appended hereto and their equivalents.

Claims (12)

About the total weight of the composition
10 to 30% by weight hydrogen peroxide;
A monocyclic heterocyclic compound containing at least one hetero atom selected from oxygen, sulfur, and nitrogen in the molecule, a heterocyclic compound having a condensed structure of the above-mentioned monocyclic heterocycle and a benzene ring, and a mixture thereof 0.1 to 5 wt% of an etch inhibitor selected;
0.1 to 5% by weight of a chelating agent;
0.1 to 5% by weight of an etching additive comprising at least one compound selected from the group consisting of inorganic acids, organic acids and salts thereof;
0.01 to 2% by weight of a fluorine compound;
0.01 to 2% by weight of an undercut inhibitor comprising a compound having at least one functional group in the group consisting of an amino group, a hydroxyl group, a carbonyl group and a methyl group in a condensed structure of pyrimidine and imidazole; And
Water to make the total weight of the composition 100%
&Lt; / RTI &gt; wherein the copper and molybdenum-containing film have a thickness of about 10 &lt; RTI ID = The method according to claim 1,
The etch inhibitor may be selected from the group consisting of furane, thiophene, pyrrole, oxazole, imidazole, pyrazole, triazole, tetrazole, 5-aminotetrazole, methyltetrazole, piperazine, methylpiperazine, hydroxyethylpiperazine, pyrrolidine, alooxanthine, and the like. The present invention relates to a process for the preparation of a compound of the formula (I) or a pharmaceutically acceptable salt thereof, including, but not limited to, alloxan, benzofurane, benzothiophene, indole, benzimidazole, benzpyrazole, tolutriazole, hydrotolutriazole ), Hydroxytolutriazole, and mixtures thereof. &Lt; Desc / Clms Page number 19 &gt; The method according to claim 1,
Wherein the chelating agent is a compound containing a carboxylic acid group or a phosphonic acid group together with an amino group in a molecule. The method according to claim 1,
The chelating agent may be selected from the group consisting of iminodiacetic acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetrinitrilacetic acid, aminotris (methylenephosphonic acid) methylenephosphonic acid), (1-hydroxyethane-1,1-diyl) bis (phosphonic acid), ethylenediamine tetra (methylenephosphonic acid) (ethylenediamine tetra (methylene phosphonic acid)), diethylenetriamine penta (methylene phosphonic acid), alanine, glutamic acid, aminobutyric acid, glycin ), And mixtures thereof. &Lt; / RTI &gt; The method according to claim 1,
Wherein the etch additive is selected from the group consisting of inorganic acids including sulfuric acid, nitric acid, and phosphoric acid; Organic acids including acetic acid, formic acid, butanoic acid, citric acid, glycolic acid, oxalic acid, malonic acid, pentanoic acid, propionic acid, tartaric acid, gluconic acid, glycosic acid and succinic acid; Salts thereof; And mixtures thereof. &Lt; / RTI &gt; The method according to claim 1,
The etch additive may be selected from the group consisting of potassium hydrogen sulfate, sodium hydrogen sulfate, sodium sulfate, sodium persulfate, potassium sulfate, potassium persulfate, Wherein the composition is a sulfate selected from the group consisting of ammonium sulfate, ammonium persulfate, and mixtures thereof. The method according to claim 1,
Wherein the fluorine compound is a compound dissociated to generate F ^- or HF ₂ ^- . The method according to claim 1,
The fluorine compound containing copper and molybdenum, is selected from _{HF, NaF, KF, AlF 3} , HBF 4, NH 4 F, NH 4 HF 2, NaHF 2, KHF 2, NH 4 BF 4 , and mixtures thereof Lt; / RTI &gt; The method according to claim 1,
Wherein the undercut inhibitor is selected from the group consisting of adenine, guanine, hypoxanthine, xanthine, theobromine, caffeine, isoguanine, uric acid, And a mixture thereof, wherein the copper and molybdenum-containing film is a purine base. The method according to claim 1,
Wherein the undercut inhibitor is adenine, guanine, isoguanine, or a mixture thereof, the copper and molybdenum containing film. The method according to claim 1,
Wherein the water is deionized water having a resistivity value of 18 M? / Cm or more. The method according to claim 1,
Wherein the composition further comprises an additive selected from the group consisting of hydrothermal stabilizers, etch stabilizers, glass etch inhibitors, and mixtures thereof.

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