KR20170120504A - Etching composition for mono-layed film or multi-layed film, and etching method using the same - Google Patents

Abstract

The present invention relates to an etching composition for etching a metal monolayer film or a metal laminated film, which realizes an etching rate higher than the conventional one and easily controls the side etching, the taper angle, the sectional shape and the pattern shape, Life. ≪ / RTI >
For this purpose, a single-layer thin film composed of a metal selected from the group consisting of copper, titanium, molybdenum and nickel or a nitrogen compound thereof, an alloy containing one or more selected from the group consisting of copper, titanium, molybdenum and nickel And an etching composition for etching a single layer film or a laminated film comprising at least two of the single layer films, wherein the etching composition comprises azole, nitric acid, peroxide and a water-soluble organic solvent.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to an etching composition for a single-layer or multilayer film and an etching method using the same,

TECHNICAL FIELD The present invention relates to an etching method using an etching composition or an electronic composition for a metal monolayer thin film or a laminated film which can be used for a flat display or the like.

Copper and copper-containing alloys, which are low resistance materials, are used for wiring materials for display devices such as flat panel displays. Copper, however, does not have sufficient adhesion with a substrate such as glass, and is also diffused into a silicon semiconductor coating. Recently, a barrier metal layer such as a titanium layer and a molybdenum layer is provided as a barrier film between a wiring material such as a substrate and a copper layer to improve the adhesion between the wiring material and the glass substrate and to prevent diffusion into the silicon semiconductor film It is known. Also disclosed is a three-layer laminated film in which a cap film is formed on an upper layer of a copper layer to prevent oxidation of the copper layer or the like.

The etching solution for the copper and titanium laminated films is an etching solution containing a hydrogen peroxide, a nitric acid, a source of a fluorine ion, an azole, a quaternary ammonium hydroxide, a hydrogen peroxide stabilizer and water and having a pH of 1.5 to 2.5 (Patent Document 1) (Patent Document 2), an etchant containing ammonium sulfate, an azole-based compound and water (Patent Document 3), a fluorine ion-containing compound, an organic acid, an ammonium salt, a fluorine compound, a powdery glycol compound, An etchant containing a source, hydrogen peroxide, a sulfate, a phosphate, an azole-based compound and water has been proposed (Patent Document 4).

The etchant for the copper and molybdenum laminated film is preferably an etching solution containing at least one selected from the group consisting of neutral salts, inorganic acids and organic acids, hydrogen peroxide and hydrogen peroxide stabilizer (Patent Document 5), hydrogen peroxide, inorganic acids containing no fluorine atoms, An etching solution containing an amine compound, an azole, a hydrogen peroxide stabilizer (patent document 6), or a compound having a base of ammonia and amino, an etching composition containing hydrogen peroxide in an aqueous medium and having a pH of 8.5 or more (patent document 7) Has been proposed.

Japanese Patent No. 5685204 Japanese Patent Application No. 2013-522901 Japanese Patent Application Laid-Open No. 2008-227508 Japanese Patent Application No. 2008-288575 Japanese Patent No. 4282927 International Patent Publication No. 2011/099624 Japanese Patent Application No. 2010-232486

The etching solution described in Patent Documents 1 and 4 to 7 has insufficient in-plane uniformity, and a large amount of irregularities may be generated on the end portion of the resist pattern. When the etching proceeds further, Resulting in a decrease in the yield of the product, and the cross-sectional shape may be undesirably deformed. In addition, the etching composition described in Patent Document 7 has a problem in use, such as a short liquid life and low storage stability. Although the peroxide sulphate is used in the etching solution described in Patent Documents 2 and 3, the end of the resist pattern tends to be uneven as compared with hydrogen peroxide when peroxide sulphate is used. Further, there is a problem that it is difficult and difficult to control the taper angle.

SUMMARY OF THE INVENTION It is therefore an object of the present invention to solve the above problem and realize an excellent etching rate of an etching composition for etching a metal monolayer thin film or a metal laminated film and to easily control side etching, taper angle, And to provide an etching composition which maintains stability and has a longer liquid life.

SUMMARY OF THE INVENTION The present inventors have made intensive studies to solve the above problems, and have found that an organic acid and chelating agent such as malonic acid used for increasing the amount of copper phenol sulfonate dissolving a phenyl element used as a stabilizer for peroxide, a neutral salt Et al. Disclose that an etching composition formed by mixing a water-soluble organic solvent with an etching composition containing peroxide improves wettability with respect to a metal substrate, Etching was performed flatly and local etching was suppressed. As a result, the present inventors reached the present invention.

That is,

[1] A single-layer thin film composed of a metal selected from the group consisting of copper, titanium, molybdenum and nickel or a nitrogen compound thereof, an alloy containing one or more selected from the group consisting of copper, titanium, molybdenum and nickel An etching composition comprising an azole, nitric acid, a peroxide and a water-soluble organic solvent, as an etching composition for etching a single layer film or a laminated film comprising one or more of the single layer film,

[2] The etching composition according to [2], wherein the water-soluble organic solvent has a vapor pressure of 2 kPa or less at 25 ° C,

[3] The etching composition according to [3], wherein the water-soluble organic solvent is selected from the group consisting of alcohol glycol, diol triol, ketone, carbonate ester,

[4] The etching composition according to [4], wherein the water-soluble organic solvent is selected from the group consisting of ethylene glycol, diethylene glycol, and propylene glycol,

[5] The etching composition according to claim 1, wherein the peroxide is selected from the group consisting of hydrogen peroxide, ammonium peroxodisulfate, sodium peroxodisulfate, and potassium peroxodisulfate.

[6] The etching composition, further comprising phosphoric acid or a phosphate,

[7] The etching composition further comprises a compound selected from the group consisting of a quaternary ammonium hydroxide and an ammonia solution.

[8] The etching composition according to any one of [1] to [6], further comprising fluorine or a fluorine compound,

[9] The etching composition, wherein the fluorine compound is selected from the group consisting of ammonium fluoride, acidic ammonium fluoride, and hydrofluoric acid,

[10] An etching composition, characterized in that the etching composition further comprises a urea compound,

[11] The etching composition according to [11], wherein the urea compound is selected from the group consisting of phenyl urea, allyl urea, 1,3-dimethyl urea and thiourea,

[12] The etching composition further comprises an organic acid,

[13] An etching composition, characterized in that the organic acid is malonic acid or citric acid,

The etching composition may contain at least one selected from the group consisting of 1 to 15 mass% of peroxide, 1 to 10 mass% of acetic acid, 0.005 to 0.2 mass% of azole, 0.05 to 1.00 mass% of fluorine compound, 1 to 50 mass% An etching composition,

[15] An etching composition for etching a laminated film, wherein the laminated film is composed of a layer of titanium / copper / titanium,

[16] An etching composition for etching a laminated film, wherein the laminated film is composed of a copper / nickel alloy / copper / titanium layer, wherein the titanium is on the substrate side,

[17] An etching composition for etching a laminated film, wherein the laminated film is composed of a single layer of copper / a single layer of molybdenum, the single layer of molybdenum being on the substrate side,

[18] The etching composition is characterized by having a pH of less than 7.0.

[19] A single-layer thin film composed of a metal selected from the group consisting of copper, titanium, molybdenum and nickel or a nitrogen compound thereof, an alloy containing one or more selected from the group consisting of copper, titanium, molybdenum and nickel Or a laminated film including one or more of the single-layered thin films is etched by using the etching composition of any one of claims 1 to 18 and etching including etching Way,

The etching method is used for a liquid crystal display, a color film touch panel, an organic EL display electronic paper, a MEMS or an IC manufacturing process or a packaging process.

The etching composition of the present invention can collectively etch the single-layer film and / or the laminated film with high wettability to the metal in the organic solvent contained in the etching composition. In addition to improving the etching rate, it is easy to control the side etching and the taper angle, and the in-plane uniformity is high, so that the etching of the resist end and the cross-sectional shape is possible.

In addition, it is possible to etch complex and precise substrates, and the etching composition has excellent stability and can be used for a long time. By supplementing the etching composition with one or more components of the etching composition of the present invention, It is possible to prolong the life of the liquid. Therefore, it can contribute to the reduction of manufacturing cost and the safety of substrate manufacturing.

Particularly, laminated films including copper and titanium, and titanium and molybdenum undercuts, which are conventionally generated in laminated films including copper and molybdenum, can be easily suppressed. Further, even when a cap film is present on a titanium layer or a molybdenum layer having a film thickness of about 100 nm or more, it has an effect of preventing extreme etching of the vicinity of the interface of the cap film. In addition, the single-layered thin film also has an effect of preventing the smoothness and cross-sectional shape of the resist pattern edge from deteriorating. In addition, even when a peroxide stabilizer or an organic acid and a chelating agent are added, there is an effect of suppressing the in-plane uniformity and the cause of generating mouse bite at the end of the resist pattern without adding a stabilizer or a pH buffer.

1 is a schematic view of a section of a Cu / Ti substrate subjected to an etching treatment,
2 is a schematic cross-sectional view of a Cu / Mo substrate underwent Mo undercut,
3 is a schematic view of a cross section of a CuNi / Cu / Ti substrate in the form of a copper alloy,
FIG. 4 is a schematic view of a cross section of the Ti substrate subjected to the etching treatment,
5 is a schematic view of a cross section of a Ti substrate in which an upper portion of Ti is extremely etched,
6 is a SEM photograph of a section of a Cu / Ti substrate having a net taper shape,
7 is an SEM photograph of a cross-section of a Cu / Mo substrate on which Mo undercut occurred,
8 is a SEM photograph of a cross-section of a CuNi / Cu / Ti substrate having a cap film in an oblong shape,
9 is an SEM photograph of a section of a Ti substrate having a net taper shape,
10 is an SEM photograph of a Ti substrate,
11 is a schematic view of a cross-sectional shape of a resist pattern edge observed by observing a substrate of CuNi / Cu / Ti etched at a diagonal upper side,
12 is a schematic view of a cross-sectional shape obtained by observing a substrate of CuNi / Cu / Ti in which the end of the resist pattern is roughly roughened at a position above the diagonal line,
13 is an SEM photograph of the cross-sectional shape of the end portion of the resist pattern observed by etching the substrate of CuNi / Cu / Ti etched at the upper diagonal line,
14 is an SEM photograph of a cross-sectional shape obtained by observing a CuNi / Cu / Ti substrate in which the end portion of the resist pattern is roughly roughened at a position above the diagonal line.

Hereinafter, embodiments of the present invention will be described in detail.

Cu / Ti is a two-layer thin film of copper and titanium in the notation of Cu / Ti, CuNi / Cu / Ti, etc. in this specification, and CuNi / Cu / Ti is an alloy of copper and nickel, copper, Layer thin film. Also, the order of lamination is that Cu / Ti is a laminate of copper on the top of titanium, CuNi / Cu / Ti means that copper is on the top of titanium and nickel alloy is on top of copper. Therefore, the layer closest to the substrate surface is a layer of titanium.

The etching composition of the present invention can be produced by applying a resist on a single layer film and / or a laminated film on a substrate, exposing and developing a desired pattern mask to form a resist pattern, etching the single layer film and / Is to form a wiring or an electrode pattern on a substrate. At this time, as shown in FIG. 11, it is preferable that the etching surface of the end portion of the copper wiring and the angle (taper angle) between the etching surface and the lower substrate are 90 degrees or less, which is a net taper shape, desirable. Particularly, in the case of a single-layer thin film such as a barrier metal layer not containing copper, for example, Ti and Mo, since a thin film is thin and a high angle of 70 ° and 80 ° does not cause a special problem in an actual substrate, Category.

Further, the distance (side etching) from the end portion of the resist to the barrier thin film disposed under the wiring is preferably within about 3 times the thickness of the laminated film, and more preferably within about 1.5 times. For example, when the thickness of Cu / Ti is 0.6 탆 (6000 Å), the thickness is preferably 2.0 μm or less, more preferably 0.9 μm or less. Further, as shown in Fig. 2, a state in which the etching of the barrier metal layer below the copper layer proceeds is called a barrier metal undercut. However, in such a state, since the undercut portion is jointly broken, it can not be used as a substrate. Therefore, etching is not preferable.

Further, as shown in FIG. 3, when the three-layered laminated film having the cap film formed on the copper layer is etched, the metal of the cap film is difficult to dissolve than copper. The state of the awning shape is also referred to as a reverse taper, and as described above, since it is in a disconnection state, it can not be used as a substrate and is not preferable for etching.

A more preferable etch state of the single layer is the same as the Ti substrate cross section shown in Fig. That is, the taper angle is in the range of 20 to 60 占 and the side etching is 0.9 占 퐉 or less.

Figure 5 shows the Ti substrate cross-sectional schematic diagram when the etchant enters the interface between the resist and Ti. This is not a desirable state, with the top of Ti being extremely etched. 10 is an SEM photograph of a Ti substrate treated with a general etching composition containing hydrogen peroxide, an ammonia solution and a phosphate. The upper portion of Ti is extremely etched and is not in a desirable state.

Figs. 11 and 12 show the shape of the end portion of the resist pattern when viewed from diagonally above. Fig. Fig. 11 shows a state where the flatness after the etching is high, and Fig. 12 shows a state where the flatness is low. In addition, it is preferable that the etched end has a high smoothness. That is, it is preferable that the etching composition clarify the above conditions.

The etching target of the etching composition of the present invention is a single-layer thin film or a laminated film of a metal deposited on a glass or silicon substrate. It is also preferable to use a laminated film comprising one or two or more single-layer thin films made of the above metal or alloy.

In one embodiment of the invention, the monolayer or laminate film comprises a nitrogen compound of a metal selected from the group consisting of copper, titanium, molybdenum and nickel. Therefore, a single-layer thin film of TiN or MoN or a laminated film containing them is preferable.

The titanium alloy or the molybdenum alloy used for the single layer film or the laminated film is mainly composed of titanium or molybdenum and may contain other metals such as aluminum, magnesium and calcium. The titanium alloy or the molybdenum alloy may be titanium or molybdenum, Molybdenum is preferably contained in an amount of 80 wt% or more, more preferably 90 wt% or more, and still more preferably 95 wt% or more.

The laminated film may be a laminate of any one of the second, third, fourth, and fifth layers, but two or three layers are preferable. The two-layer laminated film may be, but not limited to, Cu / Ti, Cu / MoTi, Cu / TiN, Cu / Mo, Cu / MoN and the like. Further, it may be a laminated film in which Ti or Mo or an alloy layer thereof is formed from a barrier metal and a Cu or Cu alloy is deposited thereon.

In addition, the three-layered laminated film is composed of Ti / Cu / Ti, Mo / Cu / Mo, Ti / Cu / TiN, Mo / Cu / MoN, CuNi / Cu / Ti, CuNi / Cu / TiN, CuMgAl / Cu / CuMgAlO / Cu / CuMgAl, and the like. When an oxide semiconductor such as IGZO is used for the channel layer, Ti, Mo, an alloy thereof, or the like is often used as a protective film because the Cu electrode is exposed in an oxygen atmosphere. However, when the above film is deposited on the copper upper layer, it is difficult to treat it with a single liquid or have a cross-sectional shape, so that it is used as a copper alloy cap film such as CuNi or CuMgAl.

In particular, the multilayer thin film including the copper layer and the molybdenum layer is widely used for wiring of a display device such as a flat display, and the etching composition of the present invention is preferable for the multilayer film. Further, in many cases, a film formed of electrodes and wiring is made of an alloy such as titanium, molybdenum, or nickel as a barrier metal or the like. Copper and a copper alloy are often formed on the barrier metal in order to suppress diffusion into silicon or the like. The etching compositions of the present invention are suitable for selective etching of copper and copper alloy films on barrier metal as well as single layer films of barrier metal.

In addition, TFT (Thin Film Transistor) controls light by a liquid crystal of a flat panel display. In the TFT, the gate electrode and the source / drain electrode are located at the lowest layer of the TFT, and the source-drain electrode is located at the upper layer. In the case of the gate electrode, in many cases, for example, a laminated film of Cu / Ti or Cu / Mo is thickly set, whereas a thickness of the source / drain electrode is set to be slightly thin. For example, the gate electrode may have a copper of 6000A and the source-drain electrode may have a copper of 3000A. However, the present invention is not limited thereto. Therefore, it is preferable to prepare the etching composition of the present invention so that it can correspond to any thickness.

The thickness of the laminated film is preferably 1000 to 8000 angstroms, more preferably 3000 to 6000 angstroms. The thickness of copper used for the laminated film is preferably 2000 to 7000 Å, more preferably 3000 to 6000 Å. The thickness of the Ti or Mo alloy used in the laminated film is preferably 100 to 1000 angstroms, more preferably 50 to 500 angstroms.

The etching composition of the present invention comprises a water-soluble organic solvent. The water-soluble organic solvent contributes to the control of the etching rate, the side etching, the taper angle and the like, and the control of the cross-sectional shape of the smoothed portion of the resist pattern edge. The water-soluble organic solvent used in the etching composition of the present invention is preferably a liquid compatible with water, preferably a water-soluble organic solvent having a steam pressure of 2 kPa or less at 25 ° C and being compatible with water Do. Further, a water-soluble organic solvent in a solid state at room temperature is excluded. Particularly preferred are alcohols, glycols, triols, ketones, amides, nitrogen-containing five-membered rings, carbonic acid esters, sulfoxides and the like. These water-soluble organic solvents may be used alone or in combination of two or more of them in the etching composition of the present invention.

The alcohol used in the etching composition of the present invention is preferably a monohydric alcohol such as methanol, ethanol, propanol, 2-propanol or 1-butanol, or a dihydric alcohol such as ethylene glycol, propylene glycol or butylene glycol. Particularly, propanol, 2-propanol and 1-butanol are preferable, and propanol and 2-propanol are more preferable.

The glycol used in the etching composition of the present invention is preferably selected from the group consisting of enylene glycol, diethylene glycol, dipropylene glycol, 1,3-propanediol, 1,3-butanediol, 2,3-butanediol, - pentanediol and the like are preferable. Particularly, diethylene glycol, dipropylene glycol, 1,3-propanediol, 1,3-butanediol, 2,3-butanediol and 1,4-butanediol are more preferable, and diethylene glycol, dipropylene glycol, 1,3 -Butanediol is particularly preferred.

The triol used in the etching composition of the present invention is preferably glycerin or the like.

The ketone used as the etching composition of the present invention is preferably acetone, ethyl methyl ketone, diethyl ketone, methyl propyl ketone, ethyl propyl ketone, dipropyl ketone and the like, more preferably acetone.

The amide used as the etching composition of the present invention is preferably N, N-dimethylformamide, N, N-dimethylacetoamido, and more preferably N, N-dimethylformamide.

The nitrogen-containing five-membered ring used in the etching composition of the present invention is preferably N-methyl-2-pyrrolidone, 2-pyrrolidinone, or 1,3-dimethyl-2-imidazolidinone. Particularly, 1,3-dimethyl-2-imidazolidinone and N-methyl-2-pyrrolidinone are more preferable.

The carbonate ester used as the etching composition of the present invention is preferably ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate and the like. Especially ethylene carbonate.

The sulfoxides used in the etching composition of the present invention include dimethylsulfoxide and the like, and dimethylsulfoxide is preferred.

The content of the water-soluble organic solvent in the etching composition of the present invention is preferably from 1 to 50% by weight, more preferably from 5 to 50% by weight, from the viewpoint of controlling the etching rate, the side etching, the taper angle and the like and the control of the cross- To 30% by weight.

The etching composition of the present invention comprises one or two or more peroxides. The peroxide has the function of oxidizing the copper wiring with an oxidizing agent. In particular, it has a function of oxidizing and dissolving molybdenum. The peroxide is preferably hydrogen peroxide, ammonium peroxodisulfuric ammonium, ammonium peroxodisulfate, sodium peroxodisulfate, potassium peroxodisulfate, and more preferably hydrogen peroxide and peroxodisulfuric ammonium sulfate. The content of the peroxide in the etching composition of the present invention is preferably from 1 to 15% by mass, more preferably from 3 to 6% by mass, so that the control of the amount of etching is easy so that the management of hydrogen peroxide is easy and a more suitable etching rate can be ensured Do.

The etching composition of the present invention comprises nitric acid. Nitric acid contributes to the dissolution of oxidized copper and the like by peroxide. The content of nitric acid in the etching composition of the present invention is preferably from 1 to 10 mass%, more preferably from 2 to 7 mass%, from the viewpoint of obtaining an appropriate etching rate and obtaining a wiring pattern after a good etching.

The etching composition of the present invention includes one or more azoles. The azoles contribute to side etching, taper angle, and cross-sectional shape control. The azoles used in the etching compositions of the present invention are selected from the group consisting of 1,2,4-1H-triazole, 1H-benzotriazole, 5-methyl-1H-benzotriazole, Triazole such as 1H-1,2,4-triazole, tetrazole such as 1H-tetrazole 5-methyl-1H-tetrazole 5-phenyl-1H-tetrazole and 5-amino- Imidazoles such as imidazole and 1H-benzimidazole, thiazoles such as 1,3-thiazole and 4-methylthiazole, and the like are preferable. Particularly, triazoles and tetrazoles are more preferable, and 1,2,4-1H-triazole, 3-amino-1H-1,2,4-triazole and 5-amino-1H-tetrazole (ATZ) Is particularly preferable.

The azole content in the etching composition of the present invention is preferably 0.005 to 0.2 mass%, more preferably 0.01 to 0.05 mass%, from the viewpoint of obtaining a favorable wiring cross-sectional shape after etching while suppressing an increase in side etching after etching.

The etching composition of the present invention preferably further comprises one or more of phosphoric acid (phosphate) or phosphoric acid compound. Phosphoric acid ions due to phosphoric acid (phosphate) or phosphoric acid compounds contribute to etching rate control and taper angle control of copper, titanium, molybdenum, nickel or their alloys. The content of phosphoric acid (phosphate) or phosphoric acid compound in the etching composition of the present invention is preferably 0.1 to 30.0 mass%, more preferably 1.0 to 4.0 mass%, from the viewpoint of easy control of the etching rate and taper angle.

The phosphoric acid ion is not particularly limited as long as it can generate phosphoric acid ions as an etching composition, but it is not particularly limited as long as it can generate phosphoric acid ions by using an acid such as phosphoric acid (phosphate), ammonium dihydrogenphosphate, ammonium phosphate, sodium dihydrogenphosphate, sodium dihydrogenphosphate, magnesium hydrogenphosphate, , Dipotassium hydrogen phosphate, calcium monohydrogenphosphate, calcium hydrogenphosphate and the like are preferable. These may be used alone or in combination. Particularly, phosphoric acid (phosphate) is more preferable in terms of ease of handling in a liquid

Further, it is preferable that the etching composition of the present invention contains one or two or more alkaline compounds. The alkaline compound contributes to pH control, improvement of wettability to fine details, and improvement of in-plane uniformity. The alkaline compound is preferably quaternary ammonium hydroxide, ammonia water or hydroxide and is preferably a hydroxide such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethyl (2-hydroxydethyl) ammonium hydroxide, lithium hydroxide, sodium hydroxide and potassium hydroxide Alkaline earth metal hydroxides such as alkali metal hydroxides, alkali metal hydroxides, alkali metal hydroxides, alkali metal hydroxides, alkali metal hydroxides, alkali metal hydroxides such as sodium hydroxide, More preferred are amines such as a carboxylate, organic amines such as ethylamine, diethylamine, triethylamine and hydroxylethylamine, and ammonia. Particularly preferred is tetramethylammonium hydroxide (TMAH).

The content of the alkaline compound in the etching composition of the present invention is preferably from 1 to 20% by mass, more preferably from 1 to 7% by mass, from the viewpoint of obtaining a good wiring cross-sectional shape after etching.

The etching composition of the present invention preferably contains one or more fluorine or fluorine compounds. Fluorine ions from fluorine or fluorine compounds contribute particularly to the etching of barrier films of titanium-based metals. The fluorine ion is not particularly limited as long as it can generate fluorine ions in the etching composition, but hydrofluoric acid, ammonium fluoride, and ammonium fluoride are preferable. These materials may be used alone or in combination. Ammonium fluoride, ammonium fluoride and hydrofluoric acid are more preferred, especially in view of their low toxicity to animals.

The content of fluorine or fluorine compound in the etching composition of the present invention is preferably 0.05 to 1.00 mass%, and more preferably 0.1 to 0.5 mass%. When the content of fluorine ions is within the above range, the etching rate of the barrier film made of a good titanium-based metal can be obtained without increasing the etching rate of the glass substrate. In this respect, when the layers including titanium are collectively etched, it is preferable that the etching composition of the present invention contains one or two or more fluorine or fluorine compounds, and titanium is etched in the laminated film containing titanium It is preferable that the etching composition of the present invention does not contain one or two or more kinds of fluorine or fluorine compounds.

Further, the etching composition of the present invention preferably contains one or more urea-based hydrogen peroxide stabilizers. The urea-based hydrogen peroxide stabilizer contributes to the inhibition of peroxide decomposition. The urea-based hydrogen peroxide stabilizer is preferably a phenyl urea, an allyl urea, a 1,3-dimethyl urea or a thiourea, and more preferably a phenyl urea. The content of the urea-based hydrogen peroxide stabilizer in the etching composition of the present invention is more preferably 0.1 to 0.3 mass% from the viewpoint that the preferable hydrogen peroxide decomposition inhibiting effect can be appropriately obtained in the range of 0.1 to 2.0 mass%.

In addition, the etching composition of the present invention preferably contains one or more organic acids. The organic acid serves as a buffer for pH adjustment in the etching composition.

The organic acids include organic acids such as ammonium salts, citric acid, sodium citrate, sodium dihydrogen citrate, sodium citrate and potassium citrate), acetic acid and its salts (for example, ammonium acetate, calcium acetate, potassium acetate and sodium acetate), tartaric acid and its salts Tris (hydroxydemethyl) aminomethane hydrochloride), malonic acid, maleic acid, maleic acid, maleic acid, maleic acid, Triammonium citrate, ammonium dihydrogen citrate, ammonium lactate, ammonium phosphate, ammonium dihydrogen phosphate and the like are preferable.

Particularly, citric acid, malonic acid, ammonium phosphate and ammonium dihydrogen phosphate are more preferable.

In addition to the above-mentioned components, the etching composition of the present invention preferably contains one or more kinds of additives commonly used in water and other etching compositions to such an extent as not to impair the effect of the etching composition. It is preferable that water is removed from metal ions, organic impurities, particle particles and the like by distillation, ion exchange treatment filter treatment, various adsorption treatments and the like. Particularly, pure water and ultrapure water are more preferable.

In a preferred orientation of the etching composition of the present invention, the etching composition of the present invention comprises a peroxide, a fluorine or fluorine compound, nitric acid, an azole, a water soluble organic solvent and water, more preferably a peroxide, a fluorine or fluorine compound, An azole alkaline compound, a water-soluble organic solvent and water, more preferably a peroxide, a fluorine or fluorine compound, nitric acid, an azole alkaline compound, phosphoric acid, a water-soluble organic solvent and water.

In one aspect, the etching compositions of the present invention comprise an etch composition comprising a peroxide, a fluorine or fluorine compound, a nitric acid, an azole alkaline compound, a urea-based hydrogen peroxide stabilizer, a water-soluble organic solvent and water, peroxides, nitric acid, azole alkaline compounds, An urea-based hydrogen peroxide stabilizer is preferably an etching composition comprising an aqueous organic solvent and water or an etching composition comprising peroxide, fluorine or fluorine compound, nitric acid, azole alkaline compound, phosphoric acid, urea hydrogen peroxide stabilizer, water-soluble organic solvent and water . The composition of the etching composition of the present invention may vary depending on the intended film.

The etching composition of the present invention preferably has a pH of less than 7 because the peroxide is readily decomposed when the pH is greater than 7. When the layer containing titanium is etched, it is preferable that the pH is 4 or less in order to easily dissolve titanium.

Further, the present invention uses the etching composition as a single layer thin film of copper, titanium, molybdenum or nickel, a single layer thin film of an alloy containing copper, titanium, molybdenum or nickel, or a laminated film comprising the single layer thin film Etching process. The method also includes a step of contacting the etching composition of the present invention and the object to be etched. The object to be etched is as described above.

The method of bringing an etching composition into contact with an object to be etched generally includes a wet (wet) method such as a method of bringing an etching composition into contact with an object by a dropping (sheet-feed spinning) process or a spraying process or a method of immersing an object in an etching composition, It is preferable to employ a method in which the etching composition is dropped (sheet-wise spinning) on the object and brought into contact with the object, and a method in which the object is immersed and brought into contact with the etching composition.

When the temperature of the etching composition is 20 캜 or higher, the etching rate is not low and the production efficiency is not very low. On the other hand, if the temperature is lower than the boiling point, the composition change can be suppressed and the etching conditions can be kept constant. In view of this, the temperature of the etching treatment is preferably 15 to 60 占 폚, more preferably 30 to 50 占 폚.

It is possible to appropriately determine the optimal processing temperature after taking into consideration that the etching rate is increased when the temperature of the etching composition is raised, while minimizing the compositional change of the etching composition.

It is also desirable to include a liquid crystal display, a color film touch panel, an organic EL display electronic paper, a MEMS or an IC manufacturing process or a packaging process.

When performing the etching, the metal generated by etching or the like is dissolved in the etching composition.

If the etching composition is continuously used, JET, S / E, and T / A change due to the dissolved metal amount and decomposition of the peroxide. When their performance changes, the cross-sectional shape changes, making it impossible to produce the same type of product. Therefore, for the purpose of cost reduction and the like, in general, a replenishing liquid is used for the purpose of using for a long time by increasing the amount of dissolution of a metal such as copper, and the replenishing liquid is added to the etching composition . In this regard, the present invention relates to the etching composition used in the present invention as one or more than one type of peroxide, nitric acid, fluorine and / or fluorine compound, TMAH or water-soluble organic solvent used in the etching composition of the present invention Can be added. This can prolong significantly the life of the general etch composition compared to the case where organic acid or peroxide, or both, is added as a replenisher.

Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples. However, the present invention is not limited by the following examples.

1. Fabrication of metal substrate

- Fabrication of Ti substrate

Titanium (Ti) was sputtered using glass as a substrate to form a barrier film made of titanium. Thereafter, a resist was applied, a pattern mask was exposed to light, and then a photoresist was printed to form a patterned titanium monolayer thin film. At this time, the thickness of Ti was 1000 angstroms.

The Ti substrates used in the following examples and comparative examples are the corresponding substrates.

- Fabrication of Cu / Ti substrate

Titanium (Ti) was sputtered using glass as a substrate to form a barrier film made of titanium. Further, copper was sputtered to form a copper wiring. Thereafter, a resist was applied, a pattern mask was exposed to light, and then a photoresist was printed to produce a copper / titanium multilayer thin film having a pattern. At this time, the thickness of Cu / Ti was 5200 Å / 250 Å. The Cu / Ti substrate used in the following Examples and Comparative Examples is the substrate.

- Fabrication of CuNi / Cu / Ti substrate

Titanium (Ti) was sputtered using glass as a substrate to form a barrier film made of titanium. Then, copper was sputtered to form a copper wiring, and copper nickel (CuNi) of a copper alloy was sputtered to form a protective film of copper. Thereafter, a resist was applied, a pattern mask was exposed to light, and then printed to produce a copper alloy / copper / titanium multilayer thin film having a pattern. At this time, the thickness of CuNi / Cu / Ti was 250 Å / 5200 Å / 250 Å. The CuNi / Cu / Ti substrate used in the following Examples and Comparative Examples is the substrate.

- Fabrication of Cu / Mo substrate

Molybdenum (Mo) was sputtered on a glass substrate to form a molybdenum barrier film. Thereafter, copper was sputtered to form a copper wiring. Thereafter, a resist was applied, a pattern mask was exposed to light, and then a photoresist was printed to produce a copper / molybdenum multilayer thin film having a pattern. At this time, the thickness of Cu / Mo was 5500 Å / 300 Å. The Cu / Mo substrate used in the following examples and comparative examples is the substrate.

2. Etching Experiment

2-1. Etching Experiment by Addition of Water Soluble Organic Solvent

(Table 1) prepared by mixing (A) hydrogen peroxide, (B) acid ammonium fluoride, (C) nitric acid, (D) 5-amino-1H-tetrazole (ATZ) and water was placed in a beaker, Lt; RTI ID = 0.0 > thermostat. ≪ / RTI > The etching composition was immersed in a 1 x 1 cm Cu / Ti substrate while stirring in a stirrer and the etching time was measured. The etching time measured at the point of time when copper and titanium disappear is defined as the shortest etching time, about 1.5 times of the shortest etching time is the actual etching time (that is, the etching time exceeding 50%, which is indicated as 50% OE) did. An etching composition prepared by adding 10, 20 and 30 wt% of dipropylene glycol (DPG) to 100 wt% of the etching composition shown in Table 1 and an etching composition without adding DPG to the etching composition shown in Table 1 were produced Respectively.

(A) Hydrogen peroxide (% by weight) 5.5 (B) Acid ammonium fluoride (wt.%) 0.35 (C) Nitric acid (wt.%) 1.0 (D) ATZ (% by weight) 0.08 water Water (% by weight) Remainder

* ATZ: 5-amino-1H-tetrazole

Then, the etching composition was placed in a beaker and immersed in each Cu / Ti substrate while stirring in an agitator, thereby conducting an etching experiment. The substrates used in the experiments were Examples 1 to 3, respectively. In Examples 1 to 3, 10, 20 and 30% by weight of DPG were added to the etching composition of Table 1, respectively, to indicate a Cu / Ti substrate used for the etching experiment. The etching time was 1.5 times the just etching time shown in Table 2, and the etching was performed at an overetching time. In addition, each Cu / Ti substrate used in the experiment was washed and dried, and the cross-sectional shape was confirmed with an SEM. The side etching amount, the taper angle, the Ti residue, the smoothness of the end portion of the resist pattern, The results are summarized in Table 2.

Cu / Ti substrate (Cu / Ti = 5200 Å / 250 Å), 50% OE. Example 1 Example 2 Example 3
additive Kinds DPG DPG DPG Addition amount
(weight%) 10 20 30 JET (s) 92 105 110 S / E (μm) 0.4 0.5 0.4 T / A (°) 45 50 55 pH One One One

* DPG: dipropylene glycol

Also. All of the examples were preferred to be Ti residues, and the smoothness of the end of the resist pattern did not have irregularities at the ends, and the cross-sectional shape was also good. An SEM photograph of Example 1 is shown in Fig.

Subsequently, the substrate was changed to a Ti substrate, an etching experiment using the above-mentioned etching composition was conducted, and each substrate was evaluated. The results are summarized in Table 3.

In Comparative Example 1, DPG was not added to the etching composition of Table 1, and 10, 20, and 30% by weight of DPG were added to the etching composition of Table 1 in Examples 4 to 6, To the Ti substrate. As a result, in the substrate of Comparative Example 1, the cross-sectional shape of Ti became a shade shape as shown in Fig. 3, although T / A could not be measured, the substrates of Examples 4 to 6 had good cross- , The smoothness of the end portion is improved, and JET can also be controlled by the addition concentration of DPG. An SEM photograph of Example 4 is shown in Fig.

Ti substrate (Ti = 1000 Å), 50% OE. Comparative Example 1 Example 4 Example 5 Example 6 additive Kinds - DPG DPG DPG Addition amount
(weight%) - 10 20 30 JET (s) 64 71 82 90 S / E (μm) 0.2 0.2 0.2 0.2 T / A (°) - 70 70 70 Ti residue A A A A Smoothness of end B A A A Sectional shape B A A A pH One One One One

* DPG: dipropylene glycol

Further, the Ti remnants show that A is good and B is bad. The smoothness of the resist pattern edge shows that A is good and B is bad. In addition, the term "defective" means that the end portion has an irregular shape. The cross-sectional shape shows that A is good and B is bad (the same applies hereinafter).

2-2. Etching Experiment by Addition of Water Soluble Organic Solvent

An etching composition in which (A) hydrogen peroxide, (B) ammonium acid fluoride, (C) nitric acid, (D) 5-amino-1H-tetrazole (ATZ), (E) tetramethylammonium hydroxide (TMAH) Table 4) etched experiments without DPG. Cu / Ti substrate, Ti substrate, and Cu / Mo substrates were used, respectively, and etching experiments were conducted under the same experimental conditions.

(A) Hydrogen peroxide (% by weight) 5.5 (B) Acid ammonium fluoride (wt.%) 0.35 (C) Nitric acid (wt.%) 4.0 (D) ATZ (% by weight) 0.08 (E) TMAH (% by weight) 4.5 water Water (% by weight) Remainder

TMAH: tetramethylammonium hydroxide

The result of etching the Cu / Ti substrate is summarized in Table 5. Comparative Example 2 refers to a Cu / Ti substrate used in the etching experiment without adding DPG to the etching composition of Table 4, and in Example 7-9, 10 to 20% by weight of DPG was added to the etching composition of Table 4, It refers to an experimental Cu / Ti substrate. As a result, it was also found that the smoothness of the end portion of the resist pattern was improved by controlling the JET and T / A by adding DPG in the laminated film.

Cu / Ti substrate (Cu / Ti = 5200 Å / 250 Å), 50% OE. Comparative Example 2 Example 7 Example 8 Example 9 additive Kinds - DPG DPG DPG Addition amount
(weight%) - 10 20 30 JET (s) 120 103 118 125 S / E (μm) 0.6 0.7 0.6 0.5 T / A (°) 35 45 45 45 Ti residue A A A A Smoothness of end B A A A Sectional shape A A A A pH One One One One

* DPG: dipropylene glycol

Table 6 shows the results of etching the substrate of Ti. In this case, Comparative Example 3 refers to the substrate of Ti used for the etching experiment without adding DPG to the etching composition of Table 4, and Examples 10 to 12 show the cases where DPG was added to the etching composition of Table 4 in amounts of 10, 20 and 30 wt% And the Ti substrate used in the etching experiment. As a result, it was found that by adding DPG, the JET can be controlled, and the smoothness and cross-sectional shape of the resist pattern edge can be improved.

Ti substrate (Ti = 1000 Å), 50% OE. Comparative Example 3 Example 10 Example 11 Example 12 additive Kinds - DPG DPG DPG Addition amount
(weight%) - 10 20 30 JET (s) 75 85 96 107 S / E (μm) 0.1 0.2 0.2 0.1 T / A (°) - 80 80 80 Ti residue A A A A Smoothness of end B A A A Sectional shape B A A A pH One One One One

* DPG: dipropylene glycol

Table 7 summarizes the results of etching the Cu / Mo substrate. In this case, Comparative Example 4 refers to a substrate of Cu / Mo used for the etching experiment without adding DPG to the etching composition of Table 4, and Examples 13 and 14 indicate that the etching compositions of Table 4 were doped with DPG in amounts of 10 and 20 wt% And the Cu / Mo substrate used in the etching experiment. As a result, JET and T / A could be controlled by addition of DPG even in the single layer film as described above. The smoothness and the cross-sectional shape of the end portions of the examples were all good.

Cu / Mo substrate (Cu / Mo = 5500 Å / 300 Å), 50% OE. Comparative Example 4 Example 13 Example 14
additive Kinds - DPG DPG Addition amount
(weight%) - 10 20 JET (s) 105 90 95 S / E (μm) 1.5 1.0 1.0 T / A (°) 15 20 25 pH One One One

* DPG: dipropylene glycol

2-3. Etching Experiment by Addition of Water Soluble Organic Solvent

(D) 5-amino-1H-tetrazole (ATZ), (E) tetramethylammonium hydroxide (TMAH), (F) phosphoric acid and water The mixed etching compositions (Table 8) were etched without DPG. Etching experiments were performed using CuNi / Cu / Ti substrates. At this time, an etching test was conducted under the same experimental conditions as above except that O.E. was 50% or 100%.

(A) Hydrogen peroxide (% by weight) 5.5 (B) Acid ammonium fluoride (wt.%) 0.35 (C) Nitric acid (wt.%) 4.0 (D) ATZ (% by weight) 0.08 (E) TMAH (% by weight) 4.5 (F) Phosphoric acid (wt%) 3.0 water Water (% by weight) Remainder

Table 9 summarizes the results of CuNi / Cu / Ti substrates treated with 50% O.E. Comparative Example 5 indicates a substrate of CuNi / Cu / Ti used in an etching experiment without adding DPG to the etching composition of Table 8, Examples 15 to 17 show that the etching compositions of Table 8 were doped with DPG at 10, 20, And 30 wt% of CuNi / Cu / Ti. As a result, it was found that JET can be controlled by adding DPG. In all of the examples, Ti residues were all good, and the smoothness of the end portions of the resist pattern did not have irregularities at the ends, and the cross-sectional shape was good.

CuNi / Cu / Ti substrate (CuNi / Cu / Ti = 250 Å / 5200 Å / 250 Å), 50% OE. Comparative Example 5 Example 15 Example 16 Example 17
additive Kinds - DPG DPG DPG Addition amount
(weight%) - 10 20 30 JET (s) 79 81 90 113 S / E (μm) 0.7 0.7 0.7 0.8 T / A (°) 50 50 60 60 pH One One One One

* DPG: dipropylene glycol

Table 10 summarizes the results of CuNi / Cu / Ti substrates treated with 100% O.E. In this case, in Comparative Example 6, the substrate of CuNi / Cu / Ti used in the etching experiment without adding DPG to the etching composition of Table 8 was used. In Examples 18 to 20, DPG was added to the etching composition of Table 8 at 10, CuNi / Cu / Ti substrate used in the etching experiment by adding Cu / Ni / Cu / Ti in weight%.

As a result, the JET can be controlled by adding DPG, and the smoothness of the resist pattern edge can be improved.

CuNi / Cu / Ti substrate (CuNi / Cu / Ti = 250 Å / 5200 Å / 250 Å), 100% OE. Comparative Example 6 Example 18 Example 19 Example 20 additive Kinds - DPG DPG DPG Addition amount
(weight%) - 10 20 30 JET (s) 79 81 90 113 S / E (μm) 1.0 1.1 1.2 1.3 T / A (°) 50 60 60 50 Ti residue A A A A Smoothness of end B A A A Sectional shape A A A A pH One One One One

* DPG: dipropylene glycol

2-4. Etching Experiment by Addition of Water Soluble Organic Solvent

(D) 5-amino-1H-tetrazole (ATZ), (E) tetramethylammonium hydroxide (TMAH), (F) phosphoric acid, (G) The etch composition (Table 11) in which the phenyl element and water were mixed was etched to include DPG.

CuNi / Cu / Ti substrates, Cu / Ti substrates, and Cu / Mo substrates. At this time, O.E. was changed to 50% or 100%, and an etching experiment was conducted under the same experimental conditions as above.

(A) Hydrogen peroxide (% by weight) 5.5 (B) Acid ammonium fluoride (wt.%) 0.35 (C) Nitric acid (wt.%) 4.0 (D) ATZ (% by weight) 0.08 (E) TMAH (% by weight) 4.5 (F) Phosphoric acid (wt%) 3.0 (G) Phenyl element (% by weight) 0.3 water Water (% by weight) Remainder

Table 12 summarizes the results of CuNi / Cu / Ti substrates treated with 50% O.E. In this case, Comparative Example 7 refers to a substrate of CuNi / Cu / Ti used in the etching experiment without adding DPG to the etching composition of Table 11. Examples 21 to 23 show that the etching compositions of Table 11 were doped with DPG at 10, And 30 wt% of CuNi / Cu / Ti.

As a result, JET, S / E and T / A could be controlled by adding DPG, and it was found that the smoothness of the resist pattern end and the cross-sectional shape could be improved. SEM photographs of Comparative Example 7 are shown in Figs. 8 and 14, and SEM photographs of Example 23 are shown in Fig.

CuNi / Cu / Ti substrate (CuNi / Cu / Ti = 250 Å / 5200 Å / 250 Å), 50% OE. Comparative Example 7 Comparative Example 8 Example 21 Example 22 Example 23 additive Kinds - DPG DPG DPG Addition amount
(weight%) - 10 20 30 JET (s) 150 130 135 95 110 S / E (μm) 7.3 13.4 1.2 0.7 0.7 T / A (°) 60 90 40 40 40 Ti residue A B A A A Smoothness of end B B A A A Sectional shape B B A A A pH One One One One One

* DPG: dipropylene glycol

Further, comparative 8 shows that an etching composition which does not mix phosphoric acid when forming the etching composition of Table 11 (i.e., (A) hydrogen peroxide, (B) ammonium acid fluoride, (C) nitric acid, (D) Tetraazoles (ATZ), (E) tetramethylammonium hydroxide (TMAH), (G) phenyl urea, and water were separately prepared, and CuNi / Cu / Ti. ≪ / RTI > From the results of Comparative Example 7 and Comparative Example 8, it was found that, in the absence of phosphoric acid, the in-plane uniformity was greatly decreased and the S / E was increased, so that the smoothness and the cross-sectional shape of the end portion were deteriorated. This is expected to be caused by the addition of phenyl elements. However, the addition of phosphoric acid to the component, that is, the addition of DPG, which is a water-soluble organic solvent, to the etching composition of Table 11 facilitates control of S / E and T / A, I can do it. In this respect, it is expected that the water-soluble organic solvent has an effect of further enhancing the effect of phosphoric acid.

The results of CuNi / Cu / Ti substrates treated with 100% O.E. are summarized in Table 13. In this case, Comparative Example 9 refers to CuNi / Cu / Ti substrate used in the etching experiment without adding DPG to the etching composition of Table 11, Examples 24 to 26 show that the etching composition of Table 11 is doped with DPG at 10, 20, 30 CuNi / Cu / Ti substrate used in the etching experiment by adding Cu / Ni / Cu / Ti in weight%.

As a result, JET, S / E and T / A could be controlled by adding DPG, and the smoothness of the resist pattern end and the cross-sectional shape could be improved.

CuNi / Cu / Ti substrate (CuNi / Cu / Ti = 250 Å / 5200 Å / 250 Å), 100% OE. Comparative Example 9 Example 24 Example 25 Example 26 additive Kinds - DPG DPG DPG Addition amount
(weight%) - 10 20 30 JET (s) 150 135 95 110 S / E (μm) 2.1 1.7 1.0 1.1 T / A (°) 50 50 40 40 Ti residue A A A A Smoothness of end B A A A Sectional shape B A A A pH One One One One

* DPG: dipropylene glycol

Table 14 summarizes the results of the Cu / Ti substrate treated with 50% O.E. Comparative Example 10 refers to the substrate of Cu / Ti used in the etching experiment without adding DPG to the etching composition of Table 11, and Examples 27 to 29 show the results of the comparison of the etching composition of Table 11 with DPG of 10, 20 and 30 wt% %, Respectively, to indicate the substrate of Cu / Ti used for the corrosion test.

As a result, JET, S / E and T / A could be controlled by adding DPG. In all of the examples, Ti residues were all good, and the smoothness of the end portions of the resist pattern did not have irregularities at the ends, and the cross-sectional shape was good.

Cu / Ti substrate (Cu / Ti = 5200 Å / 250 Å), 50% OE. Comparative Example 10 Comparative Example 11 Example 27 Example 28 Example 29 additive Kinds - DPG DPG DPG Addition amount
(weight%) - 10 20 30 JET (s) 150 150 135 110 118 S / E (μm) 11.6 18.9 1.0 0.6 0.7 T / A (°) 70 90 40 40 40 pH One One One One One

* DPG: dipropylene glycol

In Comparative Example 11, an etching composition which does not mix phosphoric acid (that is, (A) hydrogen peroxide, (B) ammonium acid fluoride, (C) nitric acid, (D) (ATZ), (E) tetramethylammonium hydroxide (TMAH), (G) phenyl urea, and water were separately prepared, and the etching rate of the Cu / Ti. ≪ / RTI >

From the results of Comparative Example 10 and Comparative Example 11, it was found that the resist pattern end and the cross-sectional shape were deteriorated due to the absence of phosphoric acid. This is presumably due to the addition of the phenyl element as described above. However, the addition of phosphoric acid to the component, that is, DPG, which is a water-soluble organic solvent, in the etching composition of Table 11 facilitates control of S / E and T / A to improve the smoothness and cross- . As a result, it can be expected that the water-soluble organic solvent has the effect of further enhancing the effect of phosphoric acid.

Table 15 summarizes the results of the Cu / Mo substrate treated with 50% O.E. In this case, Comparative Example 12 refers to a substrate of Cu / Mo used for the etching experiment without adding DPG to the etching composition of Table 11, and Examples 30 to 32 show DPGs of 10, 20 and 30 wt% % To the substrate of Cu / Mo used in the etching experiment.

As a result, JET and T / A could be controlled by adding DPG.

Cu / Mo substrate (Cu / Mo = 5500 Å / 350 Å), 50% OE. Comparative Example 12 Example 30 Example 31 Example 32 additive Kinds - DPG DPG DPG Addition amount
(weight%) - 10 20 30 JET (s) 128 125 97 110 T / A (°) Loss of resist 70 70 80 Ti residue A A A A Smoothness of end A A A A Sectional shape A A A A pH One One One One

* DPG: dipropylene glycol

2-5. Etching Experiment by Addition of Water Soluble Organic Solvent

(A) hydrogen peroxide, (C) nitric acid, (D) 5-amino-1H-tetrazole (ATZ), (E) tetramethylammonium hydroxide (TMAH), (F) phosphoric acid, An etching experiment was conducted without including DPG in one etching composition (Table 16). Etching experiments were performed using a Cu / Ti substrate. Further, the etching experiment was carried out under the same experimental conditions as above, with O.E. set at 50%.

(A) Hydrogen peroxide (% by weight) 5.5 (C) Nitric acid (wt.%) 4.0 (D) ATZ (% by weight) 0.08 (E) TMAH (% by weight) 4.5 (F) Phosphoric acid (wt%) 3.0 (G) Phenyl element (% by weight) 0.3 water Water (% by weight) Remainder

The results of the Cu / Ti substrate are summarized in Table 17. Comparative Example 13 refers to a substrate of Cu / Ti used in the etching experiment without adding DPG to the etching composition of Table 16, and Example 33 was prepared by adding 30% by weight of DPG to the etching composition of Table 16 Gt; Cu / Ti < / RTI > substrate used.

As a result, JET, S / E and T / A could be controlled by adding DPG, thereby suppressing the disappearance of the resist pattern and flattening the end of the resist pattern, and the sectional shape became a net taper. As a result, it was confirmed that the addition of water-soluble organic solvent was also effective for the Cu monolayer film.

As described above, it is general that Mo and Ti are mainly used for the barrier metal used in the Cu laminated film. However, depending on the application, an alloy of Ta or other metal or several kinds of metals may be used. In this case, when the etching composition of the present invention is used, only the single-layer thin film of Cu can be selectively etched with respect to the laminated film. In this respect, when it is possible to perform selective etching that melts only Cu, such as the etching composition of the present invention, such as when the barrier metal layer is desired to be treated with another etching composition, other etching compositions are combined and etched in two steps by the two solutions, To the S / E or T / A within the specified range.

In addition, when the substrate including titanium is collectively etched, etching can be performed in an etching composition containing fluorine or a fluorine compound. However, when a substrate containing titanium is selectively etched, fluorine or a fluorine compound is not contained Lt; RTI ID = 0.0 > etch < / RTI > composition.

Cu / Ti substrate (Cu / Ti = 5200 Å / 250 Å), 50% OE, (Cu selective etching (Cu only etched, Ti not etched) Comparative Example 14 Example 33 additive Kinds - DPG Addition amount
(weight%) - 30 JET (s) 87 98 S / E (μm) Loss of resist 0.3 T / A (°) Loss of resist 40 Ti residue - - Smoothness of end Loss of resist A Sectional shape Loss of resist A pH One One

* DPG: dipropylene glycol

2-6. Etching Experiment by Additive Addition

(A) hydrogen peroxide, (B) acid ammonium fluoride, (C) nitric acid, (D) 5-amino-1H-tetrazole (ATZ) (Table 19) in which an acidic ammonium fluoride, (C) nitric acid, (D) 5-amino-1H-tetrazole (ATZ), (H) DPG and water were mixed . Cu / Ti substrate, and Cu / Mo substrate. In addition, an etching experiment was conducted under the same experimental conditions as above, except that the O.E. was 50%. In addition, malonic acid used as an additive was added because of the buffering action of the solution and the enhancement of the solubility of Cu and Mo, and tetramethylammonium hydroxide (TMAH) was used for pH control.

(A) Hydrogen peroxide (% by weight) 5.5 (B) Acid ammonium fluoride (wt.%) 0.35 (C) Nitric acid (wt.%) 1.0 (D) ATZ (% by weight) 0.08 water Water (% by weight) Remainder

(A) Hydrogen peroxide (% by weight) 5.5 (B) Ammonium sulfonate (wt.%) 0.35 (C) Nitric acid (wt.%) 1.0 (D) ATZ (% by weight) 0.08 (H) DPG (% by weight) 20.0 water Water (% by weight) Remainder

* DPG: dipropylene glycol

The results of the Cu / Ti substrate are summarized in Table 20 and Table 21. In Comparative Examples 14 to 18, malonic acid / TMAH was added to the etching composition of Table 18 in amounts of 0/2, 2/2, 2/3, 2/4 and 2/5 wt% Ti substrate (Table 20). Examples 34 to 36 indicate Cu / Ti substrates used in the etching experiment by adding 0/0, 2/2, 2/3, and 30% by weight of malonic acid / TMAH to the etching composition of Table 19 (Table 21) .

As a result, it was found that the smoothness of the end portion of the resist pattern was improved by adding DPG. At pH 5 and above, the solubility of Ti was significantly lowered. Therefore, the pH of the Cu / Ti substrate should be below 4.

Cu / Ti substrate (Cu / Ti = 5200 Å / 250 Å), 50% OE. Comparative Example 14 Comparative Example 15 Comparative Example 16 Comparative Example 17 Comparative Example 18 Additive A
Kinds Malonic acid Malonic acid Malonic acid Malonic acid Malonic acid Addition amount
(weight%) - 2 2 2 2 Additive B
Kinds TMAH TMAH TMAH TMAH TMAH Addition amount
(weight%) 2 2 3 4 5 JET (s) Not soluble in 3 minutes 153 180 170 Ti insoluble S / E (μm) - 0.6 0.6 0.9 - T / A (°) - 50 40 50 - Ti residue - A A A - Smoothness of end - B B B - Sectional shape - A A A - pH 4 2 3 4 5

TMAH: tetramethylammonium hydroxide

Cu / Ti substrate (Cu / Ti = 5200 Å / 250 Å), 50% OE. Example 34 Example 35 Example 36 Additive A
Kinds Malonic acid Malonic acid Malonic acid Addition amount
(weight%) - 2 2 Additive B
Kinds TMAH TMAH TMAH Addition amount
(weight%) - 2 3 JET (s) 100 180 185 S / E (μm) 0.5 0.7 0.9 T / A (°) 50 50 50 Ti residue A A A Smoothness of end A A A Sectional shape A A A pH One 2 3

TMAH: tetramethylammonium hydroxide

The results of the Cu / Mo substrate are summarized in Tables 22 and 23. At this time, in Comparative Examples 19 to 24, malonic acid / TMAH was added to the etching composition of Table 18 in amounts of 0/2, 2/2, 2/3, 2/4, 2/5 and 2/6 wt% (See Table 22). Examples 37 to 39 indicate Cu / Mo substrates used in the etching experiment by adding 2/2, 2/3 and 2/4% by weight of malonic acid / TMAH to the etching composition of Table 19, respectively (Table 23).

As a result, since the composition containing DPG suppressed Mo undercut, the pH range was broader than that of the composition without DPG, and the effect of improving the S / E and sectional shape was also large. In Table 23, it was confirmed that Mo undercut did not occur at pH 4 or lower. However, in Table 22 and Table 23, when compared with the composition of pH 4, since the S / E is very small as compared with the substrate to which the DPG is added, the pH is adjusted to 5 Mo undercuts can be suppressed even at a pH of 6. In addition, it is expected that the pH of the composition will be effective at less than pH 7, since pH 7 or higher is a concern for promotion of hydrogen peroxide decomposition. An SEM photograph of the comparative example 21 is shown in Fig. 7, and an SEM photograph of the comparative example 22 is shown in Fig.

Cu / Mo substrate (Cu / Mo = 5500 Å / 300 Å), 50% OE. Comparative Example 19 Comparative Example 20 Comparative Example 21 Comparative Example 22 Comparative Example 23 Comparative Example 24 Additive A
Kinds Malonic acid Malonic acid Malonic acid Malonic acid Malonic acid Malonic acid Addition amount
(weight%) - 2 2 2 2 2 Additive B
Kinds TMAH TMAH TMAH TMAH TMAH TMAH Addition amount
(weight%) 2 2 3 4 5 6 JET (s) Cu insoluble 150 165 185 175 280 S / E (μm) - 1.1 0.7 3.6 3.6 11.9 T / A (°) - 20 30 Mo undercut Mo undercut Mo undercut Ti residue - A A A A A Smoothness of end - A A A A A Sectional shape - A A B B B pH 4 2 3 4 5 6

TMAH: tetramethylammonium hydroxide

Cu / Mo substrate (Cu / Mo = 5500 Å / 300 Å), 50% OE. Example 37 Example 38 Example 39 Additive A
Kinds Malonic acid Malonic acid Malonic acid Addition amount
(weight%) 2 2 2 Additive B
Kinds TMAH TMAH TMAH Addition amount
(weight%) 2 3 4 JET (s) 176 185 185 S / E (μm) 1.0 1.0 0.9 T / A (°) 30 30 30 Ti residue A A A Smoothness of end A A A Sectional shape A A A pH 2 3 4

TMAH: tetramethylammonium hydroxide

Next, Comparative Examples 25 to 30 shown below were prepared in the same manner as in the etching composition of Table 18 except that the etching composition which did not mix acidic ammonium fluoride (that is, (A) hydrogen peroxide, (C) nitric acid, (ATZ) and water were separately prepared, and malonic acid / TMAH was added to the etching composition in the order of 0/2, 2/2, 2/3, 2/4, 2 / 4.5 , 2/5. And 5% by weight, respectively, of the Cu / Mo substrate used in the etching experiment (Table 24). The results of Comparative Examples 25 to 30 showed a comparatively good cross-sectional shape only at pH 2 to pH 3, but Cu or Mo did not dissolve or Mo undercut occurred at different pH. In comparison with Comparative Examples 19 to 24 treated with the etching composition containing ammonium acid fluoride, acidic ammonium fluoride has an effect of suppressing the undercut of Mo, and the addition of DPG, which is a water soluble organic solvent, .

Cu / Mo substrate (Cu / Mo = 5500 Å / 300 Å), 50% OE. Comparative Example 25 Comparative Example 26 Comparative Example 27 Comparative Example 28 Comparative Example 29 Comparative Example 30 Additive A
Kinds Malonic acid Malonic acid Malonic acid Malonic acid Malonic acid Malonic acid Addition amount
(weight%) - 2 2 2 2 2 Additive B
Kinds TMAH TMAH TMAH TMAH TMAH TMAH Addition amount
(weight%) 2 2 3 4 4.5 4.5 JET (s) 170 110 170 170 180 Cu insoluble S / E (μm) 3.0 1.5 1.1 3.0 3.8 = T / A (°) Mo undercut 30 30 Mo undercut Mo undercut - Ti residue A A A A A - Smoothness of end A A A A A - Sectional shape B A B B B - pH 2 2 3 4 5 6

TMAH: tetramethylammonium hydroxide

2-7.Petting Dependent Etching Experiment

(A) hydrogen peroxide, (B) acidic ammonium fluoride, (C) nitric acid, (D) 5-amino-1H-tetrazole (ATZ) (Table 26) in which (A) ammonium acid fluoride, (C) nitric acid, (D) 5-amino-1H-tetrazole (ATZ), (H) DPG and water were mixed. Etching experiments were performed using a Cu / Ti substrate. In addition, an etching experiment was conducted under the same experimental conditions as above, except that the OE was set at 50%. In addition, citric acid used as an additive was added because of the buffering action of the solution and the improvement of the solubility of Cu and Ti, and TMAH was used for pH control.

(A) Hydrogen peroxide (% by weight) 5.5 (B) Acid ammonium fluoride (wt.%) 0.35 (C) Nitric acid (wt.%) 1.0 (D) ATZ (% by weight) 0.08 water Water (% by weight) Remainder

(A) Hydrogen peroxide (% by weight) 5.5 (B) Acid ammonium fluoride (wt.%) 0.35 (C) Nitric acid (wt.%) 1.0 (D) ATZ (% by weight) 0.08 (H) DPG (% by weight) 20.0 water Water (% by weight) Remainder

The results of the Cu / Ti substrate are summarized in Tables 27 and 28. In this case, in Comparative Examples 31 to 33, the Cu / Ti substrate used in the etching experiment was added with citric acid / TMAH in amounts of 10/2, 10/3 and 10/8 wt%, respectively, to the etching composition of Table 25 (Table 27) And Examples 40 to 42 indicate Cu / Ti substrates used in the etching experiment by adding 10/2, 10/3, and 10/8 wt% of citric acid / TMAH to the etching compositions of Table 26, respectively (Table 28).

As a result, it can be seen that the S / E ratio increases with increasing pH. However, it was found that the substrate doped with DPG suppressed the increase of the S / E ratio compared with the substrate not doped with DPG. Further, the substrate to which DPG was not added had a concave-convex shape at the end of the resist pattern, but the substrate to which DPG was added had a flat end.

Cu / Ti substrate (Cu / Ti = 5200 Å / 250 Å), 50% OE. Comparative Example 31 Comparative Example 32 Comparative Example 33 Additive A
Kinds Citric acid Citric acid Citric acid Addition amount
(weight%) 10 10 10 Additive B
Kinds TMAH TMAH TMAH Addition amount
(weight%) 2 3 8 JET (s) 180 195 510 S / E (μm) 0.5 0.5 1.2 T / A (°) 60 60 50 Ti residue A A B Smoothness of end B B B Sectional shape B B B pH 2 3 4

TMAH: tetramethylammonium hydroxide

Cu / Ti substrate (Cu / Ti = 5200 Å / 250 Å), 50% OE. Example 40 Example 41 Example 42 Additive A
Kinds Citric acid Citric acid Citric acid Addition amount
(weight%) 10 10 10 Additive B
Kinds TMAH TMAH TMAH Addition amount
(weight%) 2 3 8 JET (s) 240 205 540 S / E (μm) 0.5 0.5 0.8 T / A (°) 70 70 70 pH 2 3 4

TMAH: tetramethylammonium hydroxide

The results of the Cu / Mo substrate are summarized in Tables 29 and 30. In this case, in Comparative Examples 36 to 39, Cu / Ti substrates were used in the etching experiments by adding 10/2, 10/3, 10/8, and 10/10% by weight of citric acid / TMAH to the etching composition of Table 25 (Table 29). In Examples 43 to 46, the etching solution of Cu / Mo used in the etching experiment was prepared by adding citric acid / TMAH to the etching composition of Table 26 at 10/2, 10/3, 10/8, (Table 30).

As a result, all of the substrates treated with the composition shown in Table 25 underwent Mo undercut. When the S / E was compared, the substrate with no DPG increased in S / E with increasing pH, E was suppressed. In addition, the substrate to which DPG was not added was found to have an irregular shape at the end of the resist pattern, but the substrate to which DPG was added was smooth. All of the substrates shown in Table 29 underwent Mo undercut. However, as in the case of using malonic acid, it was suggested that the composition ratio would be controlled to suppress this.

It was also suggested to suppress S / E by adding DPG. In addition, as in the case of using malonic acid instead of citric acid, it is expected that the pH range of less than pH 7 is effective because the pH of 7 or more may promote the decomposition of the peroxide.

Cu / Mo substrate (Cu / Mo = 5500 Å / 300 Å), 50% OE. Comparative Example 36 Comparative Example 37 Comparative Example 38 Comparative Example 29 Additive A
Kinds Citric acid Citric acid Citric acid Citric acid Addition amount
(weight%) 10 10 10 10 Additive B
Kinds TMAH TMAH TMAH TMAH Addition amount
(weight%) 2 3 8 10 JET (s) 170 210 320 295 S / E (μm) 1.1 1.5 2.8 3.2

TMAH: tetramethylammonium hydroxide

Cu / Mo substrate (Cu / Mo = 5500 Å / 300 Å), 50% OE. Example 43 Example 44 Example 45 Example 46 Additive A
Kinds Citric acid Citric acid Citric acid Citric acid Addition amount
(weight%) 10 10 10 10 Additive B
Kinds TMAH TMAH TMAH TMAH Addition amount
(weight%) 2 3 8 10 JET (s) 205 225 290 300 S / E (μm) 1.1 1.1 1.1 1.3

TMAH: tetramethylammonium hydroxide

2-8. Etching Experiment by Addition of Water Soluble Organic Solvent

(A) hydrogen peroxide, (B) ammonium fluoride, (C) nitric acid, (D) 5-amino-1H-tetrazole (ATZ), (E) tetramethylammonium hydroxide (TMAH) (IPA), diethylene glycol (DEG), dimethylsulfoxide (DMSO), 1,3-butanediol (BD), 1,3-dimethyl-2-imide Etching experiments were carried out without adding DRI, N-methyl-2-pyrrolidinone (NMP), glycerin (Gly) and N, N-dimethylacetamide (DMAc). Etching experiments were performed using CuNi / Cu / Ti substrates. Further, the etching experiment was conducted under the same experimental conditions as above, with O.E. set at 50%.

(A) Hydrogen peroxide (% by weight) 5.5 (B) Acid ammonium fluoride (wt.%) 0.35 (C) Nitric acid (wt.%) 4.0 (D) ATZ (% by weight) 0.08 (E) TMAH (% by weight) 4.5 (F) Phosphoric acid (wt%) 3.0 (G) Phenyl element (% by weight) 0.3 water Water (% by weight) Remainder

Table 32 shows the results of etching the substrate of CuNi / Cu / Ti using IPA as a water-soluble organic solvent. Comparative Example 40 was a CuNi / Cu / Ti substrate provided for the etching experiment without adding IPA to the etching composition of Table 31, and Examples 47 to 49 were obtained by adding IPA to the etching composition of Table 31 at 10, 20, 30 weight % To the CuNi / Cu / Ti substrate provided for the corrosion test.

As a result, JET, S / E and T / A can be controlled as compared with the substrate without IPA, so that the end of the resist pattern is flat and the sectional shape is in the net taper.

CuNi / Cu / Ti substrate (CuNi / Cu / Ti = 250 Å / 5200 Å / 250 Å), 50% OE. Comparative Example 40 Example 47 Example 48 Example 49 additive Kinds - IPA IPA IPA Addition amount
(weight%) - 10 20 30 JET (s) 150 110 109 126 S / E (μm) 7.3 1.1 1.1 1.3 T / A (°) 60 45 45 45 Ti residue A A A A Smoothness of end B A A A Sectional shape B A A A pH One One One One

* IPA: 2-propanol

Table 33 shows the results of etching the substrate of CuNi / Cu / Ti using DEG and DMSO as water-soluble organic solvents. In Examples 50 to 52, DEG was added to the etching composition of Table 31 in amounts of 10, 20, and 30 wt%, respectively, to indicate the substrate of CuNi / Cu / Ti used in the etching experiment. And CuNi / Cu / Ti substrates used in the etching experiment by adding DMSO to the etching composition in amounts of 10, 20, and 30 wt%, respectively.

As a result, JET, S / E, and T / A could be controlled as compared to a substrate not doped with DEG and DMSO, so that the end of the resist pattern was flat and the sectional shape became a net taper shape.

CuNi / Cu / Ti substrate (CuNi / Cu / Ti = 250 Å / 5200 Å / 250 Å), 50% OE. Example 50 Example 51 Example 52 Example 53 Example 54 Example 55 additive
Kinds DEG DEG DEG DMSO DMSO DMSO Addition amount
(weight%) 10 20 30 10 20 30 JET (s) 129 113 126 115 140 138 S / E (μm) 1.8 1.4 1.2 1.3 1.5 1.5 T / A (°) 40 45 40 45 40 40 Ti residue A A A A A A Smoothness of end A A A A A A Sectional shape A A A A A A pH One One One One One One

* DEG: diethylene glycol, DMSO: dimethylsulfoxide

Table 34 shows the results of etching the substrate of CuNi / Cu / Ti using BD and DMI as water-soluble organic solvents. Examples 56 to 58 indicate substrates of CuNi / Cu / Ti provided in the etching experiment by adding 10, 20 and 30% by weight of BD, respectively, to the etching composition of Table 31, Cu / Ti / Cu / Ti substrate added to the etching composition in an amount of 10, 20 and 30 wt%, respectively, for the etching experiment.

As a result, JET, S / E and T / A can be controlled as compared with the substrate without BD and DMI, so that the end of the resist pattern is flat and the sectional shape is a net taper shape.

CuNi / Cu / Ti substrate (CuNi / Cu / Ti = 250 Å / 5200 Å / 250 Å), 50% OE. Example 56 Example 57 Example 58 Example 59 Example 60 Example 61 additive
Kinds BD BD BD DMI DMI DMI Addition amount
(weight%) 10 20 30 10 20 30 JET (s) 112 108 105 121 110 145 S / E (μm) 1.2 1.4 1.3 1.5 1.1 1.4 T / A (°) 40 45 45 40 35 40 Ti residue A A A A A A Smoothness of end A A A A A A Sectional shape A A A A A A pH One One One One One One

* BD: 1,3-butanediol, DMI: 1,3-dimethyl-2-imidazolidinone

Table 35 shows the results of etching the substrate of CuNi / Cu / Ti using NMP and Gly as water-soluble organic solvents. In Examples 62 to 64, NMP was added to the etching composition of Table 31 in amounts of 10, 20, and 30 wt%, respectively, to give CuNi / Cu / Ti substrates provided in the etching experiment. Cu / Ti / Cu / Ti substrate added to the etching composition in an amount of 10, 20, and 30 wt%, respectively.

As a result, JET, S / E and T / A could be controlled as compared with the substrate without NMP and Gly, so that the end of the resist pattern was flat and the sectional shape became a net taper shape.

CuNi / Cu / Ti substrate (CuNi / Cu / Ti = 250 Å / 5200 Å / 250 Å), 50% OE. Example 62 Example 63 Example 64 Example 65 Example 66 Example 67 additive
Kinds NMP NMP NMP Gly Gly Gly Addition amount
(weight%) 10 20 30 10 20 30 JET (s) 108 121 144 127 142 138 S / E (μm) 1.5 1.1 1.4 1.4 1.5 1.5 T / A (°) 40 45 40 40 45 45 Ti residue A A A A A A Smoothness of end A A A A A A Sectional shape A A A A A A pH One One One One One One

NMP: N-methyl-2-pyrrolidinone, Gly: glycerin

Table 36 shows the results of etching the substrate of CuNi / Cu / Ti using DMAc as a water-soluble organic solvent. Examples 68 to 70 indicate CuNi / Cu / Ti substrates provided in the etching experiment by adding 10, 20 and 30 wt% of DMAc to the etching composition of Table 31, respectively.

As a result, it can be seen that JET, S / E and T / A can be controlled as compared with a substrate to which DMAc is not added, so that the end of the resist pattern is flat and the sectional shape is a net tapering shape.

CuNi / Cu / Ti substrate (CuNi / Cu / Ti = 250 Å / 5200 Å / 250 Å), 50% OE. Example 68 Example 69 Example 70 additive
Kinds DMAc DMAc DMAc Addition amount
(weight%) 10 20 30 JET (s) 110 124 168 S / E (μm) 1.3 1.3 1.6 T / A (°) 45 50 50 Ti residue A A A Smoothness of end A A A Sectional shape A A A pH One One One

* DMAc: N, N-dimethylacetamide

In the above results, JET, S / E and T / A can be controlled using a water-soluble organic solvent, and the end of the resist pattern is flat and the sectional shape is in the form of a net taper.

2-9. Etching experiments with peroxide

An etching composition in which (A) ammonium peroxodisulfurate, (B) ammonium acid fluoride, (C) nitric acid, (D) 5-amino-1H-tetrazole (ATZ), ). ≪ / RTI > Etching experiments were performed using CuNi / Cu / Ti substrates. At this time, the etching experiment was carried out under the same experimental conditions as above with O.E. set at 50%.

(A) Peroxydic ammonium sulfate (wt.%) 5.5 (B) Acid ammonium fluoride (wt.%) 0.35 (C) Nitric acid (wt.%) 4.0 (D) ATZ (% by weight) 0.08 (G) Phenyl element (% by weight) 0.3 water Water (% by weight) Remainder

The CuNi / Cu / Ti substrate results are summarized in Table 38. Comparative Example 41 refers to the substrate of CuNi / Cu / Ti provided for the corrosion test without adding DPG to the etching composition of Table 37, Examples 71 and 72 indicate that DPG is added to the etching composition of Table 37 at 10 and 20 CuNi / Cu / Ti substrate added by weight% in the etching experiment.

As a result, it was found that the substrate doped with DPG can control JET, S / E and T / A as compared with the substrate not doped with DPG, and furthermore, the sectional shape appears as a net taper. As a result, peroxide such as peroxodisulfuric ammonium sulfate and the like can obtain a similar effect to hydrogen peroxide, so that peroxidized ammonium sulfate and the like can be substituted for hydrogen peroxide.

Cu / Ti substrate (Cu / Ti = 5200 Å / 250 Å), 50% OE. Comparative Example 41 Example 71 Example 72 additive
Kinds DPG DPG DPG Addition amount
(weight%) 10 20 30 JET (s) 55 62 76 S / E (μm) 2.2 1.9 1.9 T / A (°) 30 30 40 Ti residue A A A Smoothness of end A A A Sectional shape A A A pH One One One

* DPG: dipropylene glycol

3. Diffusion experiment of liquid life

3-1. Liquid Life Evaluation Experiment

(A) hydrogen peroxide, (B) hydrofluoric acid, (C) nitric acid, (D) 5-amino-1H-tetrazole (ATZ), (E) TMAH, An evaluation of the life of the liquid was performed using one etching composition (Table 39). The test for evaluating the life of the liquid is an experiment for confirming the change in the performance when the copper dissolution amount is increased. In addition, copper dissolution was carried out by substituting copper powder for the copper substrate. The substrate provided in the experiment was etched using CuNi / Cu / Ti substrate. At this time, the etching experiment was carried out under the same conditions as in the above experiment, in which O.E. was 50%.

(A) Hydrogen peroxide (% by weight) 5.5 (B) Hydrofluoric acid (wt.%) 0.40 (C) Nitric acid (wt.%) 5.0 (D) ATZ (% by weight) 0.07 (E) TMAH (% by weight) 7.0 (F) Phosphoric acid (wt%) 3.0 (G) Phenyl element (% by weight) 0.3 (H) DPG (% by weight) 15.0 water Water (% by weight) Remainder

* DPG: dipropylene glycol

Table 40 summarizes the CuNi / Cu / Ti substrate results. Example 74 refers to a substrate of CuNi / Cu / Ti treated with an etching composition containing no copper added to the etching composition of Table 39. Examples 75 to 77 were prepared by coating Cu, And 3000 ppm dissolved CuNi / Cu / Ti substrate treated with the etching composition.

Comparative Examples 75 to 77, which were treated with an etching composition in which copper was dissolved from 0 ppm to 2000 ppm, were gradually degraded in performance. In addition, in Example 77 treated with an etching composition in which 3000 ppm of copper was dissolved, the performance deteriorated and a Ti residue appeared. Although not shown in the following table, when copper was added to 4000 ppm, the copper itself was not completely dissolved in the etching composition.

CuNi / Cu / Ti substrate (CuNi / Cu / Ti = 250 Å / 5200 Å / 250 Å), 50% OE. Example 74 Example 75 Example 76 Example 77 additive Addition amount
(weight%) 0 1000 2000 3000 JET (s) 73 85 93 114 S / E (μm) 0.7 0.6 0.5 0.1 T / A (°) 50 50 60 50 Ti residue A A A B Smoothness of end A A A A Sectional shape A A A A pH One One One One

3-2. Diffusion experiment of liquid life

Next, while adding the composition of the etching composition (Table 41) obtained by mixing (A) hydrogen peroxide, (B) hydrofluoric acid, (C) nitric acid, (D) TMAH and water as a replenishing liquid to the etching composition of Table 39, . At this time, in the replenishment solution addition method, 1.8% by volume or 2.0% by volume of the etching composition was added to the etching composition every 1000 ppm of copper dissolved therein. The substrate provided in the experiment was etched using CuNi / Cu / Ti substrate. At this time, the etching experiment was performed under the same experimental conditions as above, with O.E. set at 50%.

Amount of supply (A) Hydrogen peroxide (% by weight) 5.5 (B) Hydrofluoric acid (wt.%) 0.40 (C) Nitric acid (wt.%) 5.0 (D) TMAH (% by weight) 0.07 water Water (% by weight) Remainder

The CuNi / Cu / Ti substrate results are summarized in Table 42. Example 78 refers to a substrate of CuNi / Cu / Ti treated with an etching composition that does not add additional copper powder and replenisher to the etching composition of Table 39, and Examples 79 to 82 show a copper / Cu / Ti substrate treated with an etching composition containing 8,000, 16,000, 24,000 and 32,000 ppm of powders, respectively, and the replenishing solutions of Table 41 were added at 14.4, 32.0, 46.8 and 62.4 vol%, respectively.

As a result, in Example 77, the Ti residue occurred at a copper dissolution amount of 3000 ppm, whereas in Example 82, the addition of 32000 ppm of copper showed no Ti residue. In addition, it has been shown that the performance is maintained almost equal to the initial performance.

It has thus been found that compositions containing peroxide, nitric acid, fluorine and / or fluorine compounds, TMAH or water-soluble organic solvents, etc., can be added to the etch composition of the present invention as a replenisher to prolong the life of the liquid.

CuNi / Cu / Ti substrate (CuNi / Cu / Ti = 250 Å / 5200 Å / 250 Å), 50% OE. Example 78 Example 79 Example 80 Example 81 Example 82 Cu powder Addition amount
(weight%) 0 8000 16000 24000 32000 Amount of supply
Addition amount
(weight%) 0 14.4 32.0 46.8 62.4 Addition amount / Cu 1000 ppm
(weight%) 0 1.8 2.0 2.0 2.0 JET (s) 73 73 70 63 74 S / E (μm) 0.6 0.7 0.7 0.8 0.8 T / A (°) 50 60 70 70 70 Ti residue A A A A A Smoothness of end A A A A A Sectional shape A A A A A pH One One One One One

Etching using the etching composition of the present invention enables batch etching of a single layer film and / or a laminated film, complicated substrate can be manufactured, and high productivity can be achieved.

In addition, a substrate manufactured by an etching method using the etching composition can be used for a planar display or the like having a higher performance. Further, by using the replenishing liquid, the life of the liquid can be prolonged, contributing to the reduction of the substrate production cost and improving the safety.

Claims (20)

A single-layer thin film composed of a metal selected from the group consisting of copper, titanium, molybdenum and nickel or a nitrogen compound thereof, and a single-layer thin film made of an alloy containing at least one selected from the group consisting of copper, titanium, molybdenum and nickel , Or an etching composition for etching a laminated film comprising one or more of the above single layer films, wherein the etching composition comprises azole, nitric acid, peroxide and a water-soluble organic solvent.
The method according to claim 1,
Wherein the water-soluble organic solvent has a vapor pressure of 2 kPa or less at 25 캜.
3. The method according to claim 1 or 2,
Wherein the water-soluble organic solvent is selected from the group consisting of alcohol glycol, diol triol, ketone, carbonic ester, and sulfoxide.
4. The method according to any one of claims 1 to 3,
Wherein the water-soluble organic solvent is selected from the group consisting of ethylene glycol, diethylene glycol, and propylene glycol.
5. The method according to any one of claims 1 to 4,
Wherein the peroxide is selected from the group consisting of hydrogen peroxide, ammonium peroxodisulfate, sodium peroxodisulfate, and potassium peroxodisulfate.
6. The method according to any one of claims 1 to 5,
Wherein the etching composition further comprises phosphoric acid or a phosphate.
7. The method according to any one of claims 1 to 6,
Wherein the etching composition further comprises a compound selected from the group consisting of a quaternary ammonium hydroxide and an ammonia solution.
8. The method according to any one of claims 1 to 7,
Wherein the etching composition further comprises fluorine or a fluorine compound.
9. The method of claim 8,
Wherein the fluorine compound is selected from the group consisting of ammonium fluoride, acidic ammonium fluoride, and hydrofluoric acid.
10. The method according to any one of claims 1 to 9,
Wherein the etching composition further comprises a urea compound.
11. The method of claim 10,
Wherein the urea compound is selected from the group consisting of phenyl urea, allyl urea, 1,3-dimethyl urea, and thiourea.
12. The method according to any one of claims 1 to 11,
Wherein the etching composition further comprises an organic acid.
13. The method of claim 12,
Wherein the organic acid is malonic acid or citric acid.
14. The method according to any one of claims 1 to 13,
Wherein the etching composition comprises 1 to 15 mass% of peroxide, 1 to 10 mass% of acetic acid, 0.005 to 0.2 mass% of azoles, 0.05 to 1.00 mass% of fluorine compound, and 1 to 50 mass% ≪ / RTI >
15. The method according to any one of claims 1 to 14,
An etching composition for etching a laminated film, wherein the laminated film is comprised of a layer of titanium / copper / titanium.
15. The method according to any one of claims 1 to 14,
An etching composition for etching a laminated film, wherein the laminated film is composed of a copper / nickel alloy / copper / titanium layer, wherein the titanium is on the substrate side.
15. The method according to any one of claims 1 to 14,
An etching composition for etching a laminated film, wherein the laminated film is composed of a single layer of copper / a single layer of molybdenum, wherein the monolayer of molybdenum is on the substrate side.
18. The method according to any one of claims 1 to 17,
Wherein the etching composition has a pH of less than 7.0.
A single layer composed of a metal selected from the group consisting of copper, titanium, molybdenum, and nickel or a nitrogen compound thereof; a single layer made of an alloy containing one or more selected from the group consisting of copper, titanium, molybdenum, A method of etching a thin film or a laminated film comprising one or more of the single-layered thin films, comprising an etching process using the etching composition according to any one of claims 1 to 18.
20. The method of claim 19,
Wherein the etching method is used for a liquid crystal display, a color film touch panel, an organic EL display electronic paper, a MEMS or an IC manufacturing process or a packaging process.

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