JP2017195311A - Composition for etching single layer film or multilayer film, or etching method by use thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an etching composition for etching a metal single layer film or metal multilayer film, which achieves an etching rate superior to conventional one, which enables the easy control of a side etching, a taper angle, a sectional shape and a pattern shape, which serves to keep the stability of a performance, and which has a longer liquid life.SOLUTION: An etching composition is arranged for etching a single layer film made of a metal selected from a group consisting of copper, titanium, molybdenum and nickel, or a nitride thereof, a single layer film made of an alloy including one or more elements selected from a group consisting of copper, titanium, molybdenum and nickel, or a multilayer film including one or more films composed of the single layer films. The etching composition comprises azole, nitric acid, a peroxide and a water-soluble organic solvent.SELECTED DRAWING: None

Description

  The present invention relates to an etching composition for a metal single layer film or a laminated film that can be used for a flat panel display or the like, or an etching method using the composition.

  As wiring materials for display devices such as flat panel displays, copper and alloys containing copper, which are materials having low resistance, are used. However, originally copper has insufficient adhesion to a substrate such as glass, and copper has the property of diffusing into the silicon semiconductor film. Therefore, recently, by providing a barrier metal layer such as a titanium layer or a molybdenum layer as a barrier film between a substrate and a wiring material such as a copper layer, the adhesion between the wiring material and the glass substrate is improved, and silicon It is known to prevent diffusion into a semiconductor film. Furthermore, in order to prevent oxidation of the copper layer or the like, there is a three-layered film in which a cap film is formed on the upper layer of the copper layer.

Examples of the etching solution for copper and titanium laminated film include hydrogen peroxide, nitric acid, fluorine ion source, azoles, quaternary ammonium hydroxide, hydrogen peroxide stabilizer and water, pH 1.5 to 2.5. Etching solution (Patent Document 1), ammonium persulfate, organic acid, ammonium salt, fluorine-containing compound, powder glycol compound, azole compound and water-containing etching solution (Patent Document 2), ammonium persulfate, azole compound and An etching solution containing water (Patent Document 3), a fluorine ion supply source, hydrogen peroxide, sulfate, phosphate, an azole compound, and water has been proposed (Patent Document 4).
Moreover, as an etching solution for copper and molybdenum laminated film, for example, an etching solution containing at least one selected from a neutral salt, an inorganic acid, and an organic acid, hydrogen peroxide, and a hydrogen peroxide stabilizer (Patent Document 5) Etching solution containing hydrogen peroxide, inorganic acid not containing fluorine atom, amine compound, azole, hydrogen peroxide stabilizer (Patent Document 6), ammonia, compound having amino group, hydrogen peroxide in aqueous medium Etching compositions (Patent Document 7) and the like that are contained in the above and have a pH exceeding 8.5 have been proposed.

Japanese Patent No. 5658204 JP2013-522901A JP 2008-227508 A JP 2008-288575 A Japanese Patent No. 4282927 International Publication No. 2011/099624 JP 2010-232486 A

In the etching solutions described in Patent Documents 1 and 4 to 7, the in-plane uniformity is not sufficient, and a large amount of unevenness may occur at the edge of the resist pattern. A mouth bite having a shape like a galling mark may occur, resulting in a decrease in yield and a roughening of the cross-sectional shape. In addition, the etching composition described in the cited document 7 has problems in terms of usability such as a short liquid life and low storage stability. In addition, in the etching solutions described in Patent Documents 2 and 3, persulfate is used. However, when persulfate is used, the resist pattern end tends to be uneven as compared with hydrogen peroxide. In addition, the taper angle is difficult to control and tends to be low.
Therefore, in the etching composition for etching a metal single layer film or a metal laminated film for solving the above problems, an excellent etching rate is realized, and side etching, taper angle, cross-sectional shape, and pattern shape are easily controlled. It is also possible to provide an etching composition having a longer liquid life while maintaining performance stability.

  The present inventors are diligently studying to solve the above problems, such as phenylurea and phenolsulfonic acid used as a stabilizer for peroxide, malonic acid used to increase the amount of copper dissolved, and the like. Etching containing peroxides as a result of research, focusing on the fact that organic acids, chelating agents, and neutral salts used to obtain pH buffering action cause in-plane uniformity degradation. We found that an etching composition created by mixing a water-soluble organic solvent with the composition can improve wettability to a metal substrate, etch the metal surface smoothly, and suppress local corrosion. As a result, the present invention has been reached.

That is, the present invention relates to the following.
[1] A metal selected from the group consisting of copper, titanium, molybdenum and nickel or a single layer film consisting of these nitrides, or one or more selected from the group consisting of copper, titanium, molybdenum and nickel An etching composition for etching a single layer film made of an alloy or a laminated film including one or more of the single layer films, comprising azole, nitric acid, peroxide and a water-soluble organic solvent, Etching composition.
[2] The etching composition according to [1], wherein the water-soluble organic solvent has a vapor pressure at 25 ° C. of 2 kPa or less.
[3] The etching composition according to [1] or [2], wherein the water-soluble organic solvent is selected from the group consisting of alcohol, glycol, diol, triol, ketone, carbonate, and sulfoxide.
[4] The etching composition according to any one of [1] to [3], wherein the water-soluble organic solvent is selected from the group consisting of ethylene glycol, diethylene glycol, and dipropylene glycol.
[5] The etching composition according to any one of [1] to [4], wherein the peroxide is selected from the group consisting of hydrogen peroxide, ammonium peroxosulfate, sodium peroxosulfate, and potassium peroxosulfate.

[6] The etching composition according to any one of [1] to [5], further including phosphoric acid or a phosphate.
[7] The etching composition according to any one of [1] to [6], further including a compound selected from the group consisting of quaternary ammonium hydroxide and aqueous ammonia.
[8] The etching composition according to any one of [1] to [7], further including fluorine or a fluorine compound.
[9] The etching composition according to [8], wherein the fluorine compound is selected from the group consisting of ammonium fluoride, acidic ammonium fluoride, and hydrofluoric acid.
[10] The etching composition according to any one of [1] to [9], further including a urea compound.

[11] The etching composition according to [10], wherein the urea compound is selected from the group consisting of phenylurea, allylurea, 1,3-dimethylurea, and thiourea.
[12] The etching composition according to any one of [1] to [11], further including an organic acid.
[13] The etching composition according to [12], wherein the organic acid is malonic acid or citric acid.
[14] 1 to 15% by mass of peroxide, 1 to 10% by mass of nitric acid, 0.005 to 0.2% by mass of azoles, 0.05 to 1.00% by mass of fluorine compound, 1 to 50 Etching composition as described in any one of said [1]-[13] containing a mass% water-soluble organic solvent.
[15] An etching composition for etching a laminated film, wherein the laminated film has a layer configuration of titanium / copper / titanium according to any one of [1] to [14]. object.

[16] An etching composition for etching a laminated film, wherein the laminated film has a layer configuration of alloy of copper and nickel / copper / titanium, and the titanium is on the substrate side. [14] The etching composition according to any one of [14].
[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, and the single layer of molybdenum is on the substrate side. The etching composition as described in any one of 1]-[14].
[18] The etching composition according to any one of [1] to [17], wherein the pH is less than 7.0.
[19] A single layer film made of a metal selected from the group consisting of copper, titanium, molybdenum and nickel or a nitride thereof, or one or more selected from the group consisting of copper, titanium, molybdenum and nickel An etching composition according to any one of [1] to [18], which is a method for etching a single layer film made of an alloy or a laminated film including one or more of the single layer films. Etching with the method.
[20] The method according to [19], which is used in a manufacturing process or a packaging process of a liquid crystal display, a color film, a touch panel, an organic EL display, electronic paper, a MEMS, or an IC.

  In the etching composition of the present invention, the wettability to metal is increased due to the organic solvent contained in the etching composition, and the single layer film and / or the laminated film can be collectively etched. In addition to improving the etching rate, the side etching and taper angle can be easily controlled, the in-plane uniformity is high, and the resist edge and the cross-sectional shape can be smoothed. The substrate can be etched. Further, the etching composition has excellent stability and can be used for a long time. Further, by replenishing the etching composition with a replenisher containing one or more components of the etching composition of the present invention, the life of the liquid can be extended while maintaining the above performance. Therefore, it can contribute to the reduction of manufacturing cost and the safety | security in board | substrate manufacture.

  In particular, it is possible to easily suppress the undercutting of titanium and molybdenum, which has been easy to occur in the past with a laminated film containing copper and titanium or a laminated film containing copper and molybdenum. In addition, even when an upper layer is further present in the titanium layer or molybdenum layer having a thickness of about 100 nm, it has an effect of preventing the vicinity of the interface of the upper layer from being etched extremely. The single layer film also has an effect of preventing deterioration of the smoothness and cross-sectional shape of the resist pattern end. In addition, the addition of peroxide stabilizers, organic acids and chelating agents suppresses the cause of in-plane uniformity degradation and the occurrence of mouth bite at the edge of the resist pattern without adding stabilizers or pH buffering agents. effective.

It is a schematic diagram of the cross section of the Cu / Ti board | substrate which carried out the etching process. It is a schematic diagram of the cross section of the Cu / Mo board | substrate with which Mo undercut generate | occur | produced. It is a schematic diagram of the cross section of the CuNi / Cu / Ti board | substrate with which the copper alloy became bowl shape.

It is a schematic diagram of the cross section of the Ti substrate which carried out the etching process. It is a schematic diagram of the cross section of Ti board | substrate with which the upper layer part of Ti was etched extremely. It is a SEM photograph of a section of a Cu / Ti substrate whose section is a forward taper.

It is a SEM photograph of the section of a Cu / Mo substrate in which Mo undercut occurred in the section. It is a SEM photograph of the section of a CuNi / Cu / Ti substrate where the upper layer part of a section became bowl shape. It is a SEM photograph of a section of a Ti substrate whose section is a forward taper shape. It is a SEM photograph of a Ti substrate.

It is the schematic diagram of the cross-sectional shape of the resist pattern edge part which observed the CuNi / Cu / Ti board | substrate etched from diagonally upward. It is the schematic diagram of the cross-sectional shape which observed the CuNi / Cu / Ti board | substrate with which the resist pattern edge part roughened unevenly from diagonally upward.

It is the SEM photograph of the cross-sectional shape of the resist pattern edge part which observed the CuNi / Cu / Ti board | substrate etched from diagonally upward. It is the SEM photograph of the cross-sectional shape which observed the CuNi / Cu / Ti board | substrate with which the resist pattern edge part roughened unevenly from diagonally upward.

Hereinafter, embodiments of the present invention will be described in detail.
In this specification, for example, Cu / Ti, CuNi / Cu / Ti, and the like may be indicated, but Cu / Ti indicates a two-layer film of copper and titanium, and CuNi / Cu / Ti is: 3 shows a three-layer film of an alloy of copper and nickel, copper and titanium. The order of the layers is that Cu / Ti has copper laminated on the upper layer of titanium, CuNi / Cu / Ti has copper on the upper layer of titanium, and an alloy of nickel on the copper. Represents that. Therefore, the layer closest to the substrate surface represents that any of the above laminated films is a titanium layer.

  In the etching composition of the present invention, a resist is applied to a single layer film and / or a laminated film on a substrate, a desired pattern mask is exposed and transferred, and developed to form a resist pattern. And / or the laminated film is etched, and finally, a wiring or an electrode pattern is formed on the substrate. In this respect, as shown in FIG. 1, the performance required for etching is preferably less than 90 ° in which the angle (taper angle) formed between the etching surface of the copper wiring end and the underlying substrate becomes a forward taper shape, -60 ° is more preferred. In particular, in the case of a barrier metal layer that does not contain copper, for example, a single layer film such as Ti or Mo, since the film thickness is thin, no particular problem occurs in an actual substrate even at a high angle of 70 ° or 80 °. For this reason, the forward tapered shape falls within a preferred range.

  Further, the distance (side etching) from the resist end to the barrier film provided under the wiring is preferably within about three times the film thickness of the laminated film. More preferably, it is within about 1.5 times. For example, if the film thickness of Cu / Ti is 0.6 μm (6000 mm), it is preferably within 2.0 μm, more preferably within 0.9 μm. Further, as shown in FIG. 2, a state in which the etching of the barrier metal layer below the copper layer has progressed is called a so-called barrier metal undercut. In such a state, the undercut portion becomes a cavity and is disconnected. Therefore, it cannot be used as a substrate. Therefore, it is not preferable as etching.

  Also, as shown in FIG. 3, when etching a three-layered film in which a cap film is formed on a copper layer, if the metal of the cap film is harder to dissolve than copper, it may become a bowl-like shape. is there. The saddle-like state is also referred to as reverse taper, and is not preferable as etching because it is disconnected as described above and cannot be used as a substrate. A more preferable etching state of the single layer is as shown in the cross-sectional view of the Ti substrate shown in FIG. That is, it has a forward taper shape with a taper angle of 20 to 60 °, and the side etching is 0.9 μm or less. The state when the etching solution enters the interface between the resist and Ti is shown in a schematic diagram of a cross section of the Ti substrate as shown in FIG. Although the upper layer part of Ti will be in the state etched extremely, naturally, it is not a preferable state. FIG. 10 is an SEM photograph of a Ti substrate treated with a general etching composition containing hydrogen peroxide, aqueous ammonia and phosphate. The upper layer portion of Ti is extremely etched, which is not a preferable state.

  Further, FIG. 11 and FIG. 12 show the shape of the resist pattern edge when observed from obliquely above. FIG. 11 shows a state where the smoothness of the end portion is high after etching, and FIG. 12 shows a state where the smoothness is low. Note that it is preferable that the end portion after etching has higher smoothness. That is, the etching composition is preferably one that satisfies the above conditions.

  The etching composition of the present invention is a metal single layer film or laminated film formed on a glass or silicon substrate. Further, it may be a laminated film including one or more single-layer films made of the above metals or alloys.

  In one embodiment of the present invention, the single-layer film or the stacked film includes a metal nitride selected from the group consisting of copper, titanium, molybdenum, and nickel. A single layer film of TiN or MoN or a laminated film including these is preferable.

  Needless to say, the titanium alloy and molybdenum alloy used for the single layer film or laminated film may contain other metals such as aluminum, magnesium, and calcium, although titanium and molybdenum are the main components. Further, the titanium alloy or the molybdenum alloy contains 80% by weight or more of titanium or molybdenum, respectively, preferably 90% by weight or more, more preferably 95% by weight or more based on the alloy weight.

  The laminated film may be any of 2, 3, 4, and 5 layers, but 2 and 3 layers are preferable. Examples of the two-layered film include, but are not limited to, Cu / Ti, Cu / MoTi, Cu / TiN, Cu / Mo, and Cu / MoN. A laminated film in which Ti, Mo, or an alloy layer thereof is formed as a barrier metal and Cu or Cu alloy is further formed thereon may be used.

  In addition, the laminated film of three layers is Ti / Cu / Ti, Mo / Cu / Mo, Ti / Cu / TiN, Mo / Cu / MoN, CuNi / Cu / Ti, CuNi / Cu / TiN, CuMgAl / Cu / CuMgAl , CuMgAlO / Cu / CuMgAl, and the like, but are not limited thereto. When an oxide semiconductor such as IGZO is used for the channel layer, since the Cu electrode is exposed in an oxygen atmosphere, Ti, Mo, or an alloy thereof is often used as a protective film. However, when these films are formed on the upper layer of copper, it is difficult to process with one solution and to make the cross-sectional shape uniform, so a copper alloy such as CuNi or CuMgAl is used as the cap film.

  In particular, a multilayer thin film including a copper layer and a molybdenum layer is often used for wiring of a display device such as a flat panel display, and the etching composition of the present invention is suitable for the multilayer film. In addition, for films formed for electrodes and wiring, alloys such as titanium, molybdenum and nickel are often used as a single layer film as a barrier metal, and copper and copper alloys are used to suppress diffusion into silicon and the like. Is often formed on the barrier metal. The etching composition of the present invention is suitable not only for the barrier metal single layer film but also for the selective etching of copper or copper alloy film on the barrier metal.

  Further, it is a TFT (Thin Film Transistor) that controls light by the liquid crystal of the flat panel display. A TFT has a gate electrode and source / drain electrodes. The gate electrode is located in the lowermost layer of the TFT, and the source / drain electrodes are located in the upper layer. From the viewpoint of electrical characteristics, for example, the gate electrode is often set to be a thicker layer of Cu / Ti or Cu / Mo, whereas the source / drain electrode is sometimes set to be slightly thinner. For example, the copper of the gate electrode is 6000% and the copper of the source / drain electrode is 3000%, but is not limited thereto. Therefore, it is preferable to prepare the etching composition of the present invention so that both film thicknesses can be handled.

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

  The etching composition of the present invention contains a water-soluble organic solvent. The water-soluble organic solvent contributes to control of the etching rate, side etching, taper angle, etc., smoothing of the resist pattern end, and control of the cross-sectional shape. The water-soluble organic solvent used in the etching composition of the present invention is preferably a liquid that is compatible with water, and a water-soluble organic solvent that has a vapor pressure at 25 ° C. of 2 kPa or less and is compatible with water is preferable. The water-soluble organic solvent in a solid state at room temperature is excluded. In particular, alcohols, glycols, triols, ketones, amides, nitrogen-containing five-membered rings, carbonates, sulfoxides and the like are more preferable. Needless to say, one or more of these water-soluble organic solvents may be used in the etching composition of the present invention.

  Furthermore, 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. In particular, 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 diethylene glycol, dipropylene glycol, 1,3-propanediol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, 1,5- Pentanediol and the like are preferable. In particular, 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, and 1,3-butane. Diols are particularly preferred.

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

  The ketone used in the etching composition of the present invention is preferably acetone, ethyl methyl ketone, diethyl ketone, methyl propyl ketone, ethyl propyl ketone, dipropyl ketone or the like. In particular, acetone is more preferable.

  The amide used in the etching composition of the present invention is preferably N, N-dimethylformamide, N, N-dimethylacetamide or the like. In particular, N, N-dimethylformamide is more preferable.

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

  The carbonic acid ester used in the etching composition of the present invention is preferably ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, or the like. In particular, ethylene carbonate is more preferable.

  Examples of the sulfoxide used in the etching composition of the present invention include dimethyl sulfoxide, and dimethyl sulfoxide is preferable.

  The content of the water-soluble organic solvent in the etching composition of the present invention can appropriately control the etching rate, side etching, taper angle, etc., smoothing of the resist pattern edge, and control of the cross-sectional shape. From 1 to 50% by mass is preferable, and 5 to 30% by mass is more preferable.

  The etching composition of the present invention contains one or more peroxides. The peroxide has a function of oxidizing copper wiring as an oxidizing agent. In particular, molybdenum has a function of oxidizing and dissolving. The peroxide is preferably hydrogen peroxide, ammonium peroxodisulfate, ammonium peroxosulfate, sodium peroxosulfate, or potassium peroxosulfate, and more preferably hydrogen peroxide or ammonium peroxodisulfate. The content of the peroxide in the etching composition of the present invention is 1 to 15% by mass, which makes it easy to control the etching amount from the viewpoint of easy management of hydrogen peroxide and securing an appropriate etching rate. Is preferable, and 3-6 mass% is more preferable.

  The etching composition of the present invention contains nitric acid. Nitric acid contributes to dissolution of copper or the like oxidized by peroxide. The content of nitric acid in the etching composition of the present invention is preferably 1 to 10% by mass, and 2 to 7% by mass from the viewpoint that an appropriate etching rate can be obtained and a good wiring shape after etching can be obtained. More preferred.

  The etching composition of the present invention contains one or more azoles. Azole contributes to the control of side etching, taper angle, and cross-sectional shape. The azoles used in the etching composition of the present invention are 1,2,4-1H-triazole, 1H-benzotriazole, 5-methyl-1H-benzotriazole, 3-amino-1H-triazole and 3-amino-1H- Triazoles such as 1,2,4-triazole, 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole and tetrazole such as 5-amino-1H-tetrazole, 1H-imidazole and 1H-benzimidazole Preferred are thiazoles such as imidazole, 1,3-thiazole and 4-methylthiazole. In particular, triazole and tetrazole are more preferable, and 1,2,4-1H-triazole, 3-amino-1H-1,2,4-triazole and 5-amino-1H-tetrazole (ATZ) are particularly preferable.

  The content of azole in the etching composition of the present invention is 0.005 to 0.2% by mass from the viewpoint that a good wiring cross-sectional shape after etching can be obtained while suppressing an increase in side etching after etching. Is preferable, and 0.01-0.05 mass% is more preferable.

  The etching composition of the present invention may further contain one or more of phosphoric acid (phosphate) or a phosphoric acid compound. Phosphate ions derived from phosphoric acid (phosphate) or phosphate compounds contribute to control of the etching rate and taper angle 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% by mass from the viewpoint of easy control of the etching rate and taper angle. 1.0-4.0 mass% is more preferable.

  The phosphate ion is not particularly limited as long as it generates phosphate ion in the etching composition, but phosphoric acid (phosphate), ammonium dihydrogen phosphate, diammonium hydrogen phosphate, sodium dihydrogen phosphate Preferred are disodium hydrogen phosphate, magnesium monohydrogen phosphate, magnesium dihydrogen phosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, calcium monohydrogen phosphate, calcium dihydrogen phosphate, and the like. Needless to say, these can be used alone or in combination. In particular, phosphoric acid (phosphate) is more preferable because it is easy to handle due to the liquid.

  The etching composition of the present invention may further contain one or more alkaline compounds. The alkaline compound contributes to pH control, improvement of wettability to fine parts, and improvement of in-plane uniformity. The alkaline compound is preferably quaternary ammonium hydroxide, aqueous ammonia or hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethyl (2-hydroxyethyl) ammonium hydroxide, lithium hydroxide, sodium hydroxide. And alkali metal hydroxides such as potassium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide, strontium hydroxide and barium hydroxide, carbonates of alkali metals such as ammonium carbonate, lithium carbonate, sodium carbonate and potassium carbonate Salts, quaternary ammonium hydroxides such as tetramethylammonium hydroxide and choline, organic amines such as ethylamine, diethylamine, triethylamine and hydroxyethylamine, and ammonia. Ri preferred. In particular, tetramethylammonium hydroxide (TMAH) is particularly preferable.

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

  The etching composition of the present invention may further contain one or more of fluorine or a fluorine compound. Fluorine ions derived from fluorine or a fluorine compound contribute particularly to etching of a barrier film made of a titanium-based metal. Fluorine ions are not particularly limited as long as they generate fluorine ions in the etching composition, but hydrofluoric acid, ammonium fluoride, ammonium acid fluoride, and the like are preferable. It goes without saying that the above substances can be used alone or in combination. In particular, ammonium fluoride, acidic ammonium fluoride, and hydrofluoric acid are more preferable from the viewpoint of low toxicity to animals.

  0.05-1.00 mass% is preferable, and, as for content of the fluorine or fluorine compound in the etching composition of this invention, 0.1-0.5 mass% is more preferable. When the fluorine ion content is within the above range, a good etching rate of the barrier film made of a titanium metal can be obtained without increasing the corrosion rate of the glass substrate. In this regard, when the layer containing titanium is collectively etched, the etching composition of the present invention preferably further contains one or more of fluorine or a fluorine compound, and titanium is removed from the laminated film containing titanium. When selectively etching only other layers without etching, it is preferable that the etching composition of the present invention does not contain one or more of fluorine or a fluorine compound.

  The etching composition of the present invention may further contain one or more urea-based hydrogen peroxide stabilizers. The urea-based hydrogen peroxide stabilizer contributes to suppression of peroxide decomposition. The urea-based hydrogen peroxide stabilizer is preferably phenylurea, allylurea, 1,3-dimethylurea, thiourea or the like, and more preferably phenylurea. The content of the urea-based hydrogen peroxide stabilizer in the etching composition of the present invention is preferably 0.1 to 2.0% by mass, and is 0 from the viewpoint that an effect of inhibiting the decomposition of hydrogen peroxide can be appropriately obtained. 0.1 to 0.3% by mass is more preferable.

  The etching composition of the present invention may further contain one or more organic acids. The organic acid has a role as a buffer for adjusting pH in the etching composition. Organic acids are ammonium salt, citric acid, sodium citrate, sodium dihydrogen citrate, disodium citrate and potassium citrate), acetic acid and its salts (eg ammonium acetate, calcium acetate, potassium acetate and sodium acetate), Tartaric acid and its salts (eg sodium tartrate, sodium hydrogen tartrate and potassium sodium tartrate), tris (hydroxymethyl) aminomethane (Tris) and its salts (eg tris (hydroxymethyl) aminomethane hydrochloride), malonic acid, citric acid Triammonium acid, ammonium dihydrogen citrate, ammonium lactate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate and the like are preferable. In particular, citric acid, malonic acid, diammonium hydrogen phosphate, and ammonium dihydrogen phosphate are more preferable.

  In addition to the above-described components, the etching composition of the present invention may further contain water and other one or more kinds of additives usually used in the etching composition to the extent that the effect of the etching composition is not impaired. . The water is preferably one from which metal ions, organic impurities, particle particles, and the like have been removed by distillation, ion exchange treatment, filter treatment, various adsorption treatments, and the like, and pure water and ultrapure water are particularly preferred.

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

  In one aspect of the etching composition of the present invention, an etching composition comprising a peroxide, fluorine or a fluorine compound, nitric acid, azole, alkaline compound, urea hydrogen peroxide stabilizer, water-soluble organic solvent and water, peroxide Etching composition containing nitric acid, azole, alkaline compound, phosphoric acid, urea hydrogen peroxide stabilizer, water-soluble organic solvent and water, or peroxide, fluorine or fluorine compound, nitric acid, azole, alkaline compound, phosphoric acid An etching composition comprising a urea-based hydrogen peroxide stabilizer, a water-soluble organic solvent and water is preferred. The etching composition of this invention can change the composition according to the film | membrane made into object.

  When the etching composition of the present invention is larger than pH 7, it is preferably less than pH 7 from the viewpoint that peroxide is easily decomposed. In addition, when etching a layer containing titanium, the pH is preferably 4 or less because titanium is easily dissolved.

  Next, the method of etching a single layer film made of copper, titanium, molybdenum or nickel, a single layer film of an alloy containing copper, titanium, molybdenum or nickel or a laminated film containing the single layer film according to the present invention includes: Etching with the etching composition. Furthermore, the process of making the etching composition of this invention and an etching target object contact is included. The etching object is as described above.

  In addition, the method of bringing the etching composition into contact with the object to be etched is usually a method of bringing the etching composition into contact with the object in the form of dripping (single wafer spin treatment) or spraying, or immersing the object in the etching composition. A wet etching method such as a method of allowing the etching composition to be used can be employed, but a method in which the etching composition is dropped onto the object (single-leaf spin treatment) and brought into contact with the object, and the object is immersed in the etching composition and brought into contact with the object The method is preferred.

  When the temperature of the etching composition is 20 ° C. or higher, the etching rate does not become too low, and the production efficiency does not significantly decrease. 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. From this point, the temperature of the etching treatment is preferably 15 to 60 ° C, and more preferably 30 to 50 ° C. Although the etching rate is increased by increasing the temperature of the etching composition, on the other hand, the optimum processing temperature can be appropriately determined in consideration of keeping the composition change of the etching composition small. .

  Furthermore, a manufacturing process or a packaging process of a liquid crystal display, a color film, a touch panel, an organic EL display, electronic paper, a MEMS, or an IC may be included.

  When etching is performed, 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 amount of dissolved metal and decomposition of peroxide. If these performances change, the cross-sectional shape also changes, making it impossible to continue making the same type of product. Therefore, in order to reduce costs, a replenisher is usually used for a long time by increasing the amount of dissolution of metals such as copper, and the replenisher is consumed by increasing the amount of dissolved metal. Used by adding to the etching composition to replenish the acid. In this regard, in the present invention, one or more peroxides, nitric acid, fluorine and / or fluorine compounds, TMAH or water-soluble organic solvents used in the etching composition of the present invention are used as a replenisher. Can be added to the used etching composition. As a result, the liquid life can be greatly extended as compared with the case where a normal etching composition is added as a replenisher using only an organic acid, a peroxide, or both.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples and the like.

1. Production of Metal Substrate and Production of Ti Substrate Glass was used as a substrate, and titanium (Ti) was sputtered to form a barrier film made of titanium. Next, a resist was applied, and the pattern mask was exposed and transferred, followed by development to produce a titanium single layer thin film having a pattern formed thereon. The film thickness of Ti was 1000 mm. The Ti substrate used in the following examples and comparative examples refers to the substrate.

-Preparation of Cu / Ti substrate Using glass as a substrate, titanium (Ti) was sputtered to form a barrier film made of titanium. Further, copper was sputtered to form a copper wiring. Next, a resist was applied, the pattern mask was exposed and transferred, and then developed to produce a copper / titanium multilayer thin film having a pattern formed thereon. The film thickness of Cu / Ti was 5200/250 mm. In addition, the Cu / Ti board | substrate used for the following example and the comparative example is the said board | substrate.

-Production of CuNi / Cu / Ti substrate Using glass as a substrate, titanium (Ti) was sputtered to form a barrier film made of titanium. Next, copper was sputtered to form copper wiring, and copper alloy copper nickel (CuNi) was sputtered to form a copper protective film. Next, a resist was applied, the pattern mask was exposed and transferred, and then developed to produce a copper alloy / copper / titanium multilayer thin film having a pattern formed thereon. The film thickness of CuNi / Cu / Ti was 250/5200/250 mm. Note that the CuNi / Cu / Ti substrates used in the following examples and comparative examples are the substrates.

-Production of Cu / Mo substrate Using glass as a substrate, molybdenum (Mo) was sputtered to form a barrier film made of molybdenum. Subsequently, copper was sputtered to form a copper wiring. Next, a resist was applied, the pattern mask was exposed and transferred, and then developed to produce a copper / molybdenum multilayer thin film having a pattern formed thereon. The film thickness of Cu / Mo was 5500/300 mm. In addition, the Cu / Mo board | substrate used for the following Examples and comparative examples is the said board | substrate.

2. Etching test 2-1. Etching test with addition of water-soluble organic solvent (A) Hydrogen peroxide, (B) acidic ammonium fluoride, (C) nitric acid, (D) 5-amino-1H-tetrazole (ATZ) and water-mixed etching composition ( Table 1) was placed in a beaker and the temperature was stabilized in a thermostatic bath maintained at 35 ° C. While stirring the etching composition with a stirrer, a 1 × 1 cm Cu / Ti substrate was immersed, and the etching time was measured. The etching time measured when copper and titanium disappeared is the just etching time, and about 1.5 times the just etching time is the actual etching time (that is, 50% overetching time, which is 50% OE). .). DPG is added to the etching composition in which 10, 20, and 30% by weight of dipropylene glycol (DPG) are added to 100% by weight of the etching composition described in Table 1, and to the etching composition described in Table 1, respectively. An etching composition was added that was not added.

Next, each of the above etching compositions was put in a beaker, and each Cu / Ti substrate was immersed while stirring with a stirrer to perform an etching test. Each board | substrate used for the test was made into Examples 1-3, respectively. In addition, Examples 1-3 point out the Cu / Ti board | substrate which added DPG to the etching composition of Table 1 by 10, 20, and 30 weight%, respectively and was used for the etching test. The etching time was 1.5 times the just etching time listed in Table 2, and etching was performed. Furthermore, each Cu / Ti substrate subjected to the test was washed with water and dried, then the cross-sectional shape was confirmed by SEM, the side etching amount of each substrate, taper angle, Ti residue, smoothness of resist pattern edge, cross-sectional shape Each performance was evaluated. The results are summarized in Table 2.

  In each of the examples, the Ti residue was good, the smoothness of the resist pattern end was not uneven, and the cross-sectional shape was good. Moreover, the SEM photograph of Example 1 is shown in FIG.

Next, the substrate was changed to a Ti substrate, an etching test was performed using the same etching composition as described above, and each substrate was evaluated. The results are summarized in Table 3. In addition, Comparative Example 1 refers to a Ti substrate subjected to an etching test without adding DPG to the etching composition of Table 1, and Examples 4 to 6 include DPG in the etching composition of Table 1 and 10 and 20 respectively. , And refers to a Ti substrate added by 30 wt% and subjected to an etching test. As a result, in the substrate of Comparative Example 1, the cross-sectional shape of Ti became a bowl shape as shown in FIG. 3, and T / A could not be measured. However, it was shown that the cross-sectional shape of the substrates of Examples 4 to 6 was improved by adding DPG, the smoothness of the edge was improved, and JET could be controlled by the addition concentration of DPG. . Moreover, the SEM photograph of Example 4 is shown in FIG.

  The Ti residue indicates that A is good and B is bad. As for the smoothness of the edge of the resist pattern, A indicates good and B indicates poor. In addition, a defect means that the edge part is uneven | corrugated. As for the cross-sectional shape, A represents good and B represents poor (hereinafter the same).

2-2. Etching test by addition of water-soluble organic solvent (A) Hydrogen peroxide, (B) Acidic ammonium fluoride, (C) Nitric acid, (D) 5-Amino-1H-tetrazole (ATZ), (E) Tetramethylammonium hydroxide Etching tests were performed with and without DPG added to the etching composition (Table 4) in which (TMAH) and water were mixed. Etching tests were performed under the same test conditions as above using Cu / Ti substrates, Ti substrates, and Cu / Mo substrates, respectively.

The results of etching the Cu / Ti substrate are summarized in Table 5. Comparative Example 2 refers to a Cu / Ti substrate subjected to an etching test without adding DPG to the etching composition of Table 4, and Examples 7 to 9 include DPG in the etching composition of Table 4 and 10 and 20 respectively. , 30% by weight, and refers to a Cu / Ti substrate subjected to an etching test. As a result, it was shown that JET and T / A can be controlled by adding DPG in the laminated film, and the smoothness of the resist pattern edge can be improved.

The results of etching the Ti substrate are summarized in Table 6. In addition, Comparative Example 3 refers to a Ti substrate subjected to an etching test without adding DPG to the etching composition of Table 4, and Examples 10 to 12 include DPG in the etching composition of Table 4 and 10 and 20 respectively. , And refers to a Ti substrate added by 30 wt% and subjected to an etching test. As a result, it was shown that JET can be controlled by adding DPG, and the smoothness and cross-sectional shape of the resist pattern edge can be improved.

The results of etching the Cu / Mo substrate are summarized in Table 7. Comparative Example 4 refers to a Cu / Mo substrate subjected to an etching test without adding DPG to the etching composition of Table 4, and Examples 13 and 14 have DPG of 10 in each of the etching compositions of Table 4. The Cu / Mo board | substrate which added 20 weight% at a time and was used for the etching test is pointed out. The results showed that JET and T / A can be controlled by adding DPG even in a single layer film as described above. In addition, the smoothness and the cross-sectional shape of the end portion of each example were both good.

2-3. Etching test by addition of water-soluble organic solvent (A) Hydrogen peroxide, (B) Acidic ammonium fluoride, (C) Nitric acid, (D) 5-Amino-1H-tetrazole (ATZ), (E) Tetramethylammonium hydroxide Etching tests were conducted with (TMAH), (F) phosphoric acid and water mixed etching compositions (Table 8) with and without DPG. An etching test was performed using a CuNi / Cu / Ti substrate. O. E. The etching test was performed under the same test conditions as above except that the ratio was set to 50% or 100%.

50% O.D. E. Table 9 summarizes the results of the CuNi / Cu / Ti substrates treated with the above. Comparative Example 5 refers to a CuNi / Cu / Ti substrate subjected to an etching test without adding DPG to the etching composition of Table 8, and Examples 15 to 17 include DPG in the etching composition of Table 8. It refers to a CuNi / Cu / Ti substrate added by 10, 20, and 30% by weight, respectively, and subjected to an etching test. The results showed that JET can be controlled by adding DPG. In each of the examples, the Ti residue was good, the smoothness of the resist pattern end was not uneven, and the cross-sectional shape was good.

100% O.D. E. Table 10 summarizes the results of the CuNi / Cu / Ti substrates treated with the above. Comparative Example 6 refers to a CuNi / Cu / Ti substrate subjected to an etching test without adding DPG to the etching composition of Table 8, and Examples 18 to 20 include DPG in the etching composition of Table 8. It refers to a CuNi / Cu / Ti substrate added by 10, 20, and 30% by weight, respectively, and subjected to an etching test. The results show that JET can be controlled and the smoothness of the resist pattern edge can be improved by adding DPG.

2-4. Etching test by addition of water-soluble organic solvent (A) Hydrogen peroxide, (B) Acidic ammonium fluoride, (C) Nitric acid, (D) 5-Amino-1H-tetrazole (ATZ), (E) Tetramethylammonium hydroxide Etching tests were performed with (TMAH), (F) phosphoric acid, (G) phenylurea and water mixed with and without DPG added to the etching composition (Table 11). Etching tests were performed using CuNi / Cu / Ti substrates, Cu / Ti substrates, and Cu / Mo substrates. O. E. Was changed to 50% or 100%, and an etching test was conducted under the same test conditions as described above.

50% O.D. E. Table 12 summarizes the results of the CuNi / Cu / Ti substrates treated with the above. Comparative Example 7 refers to a CuNi / Cu / Ti substrate subjected to an etching test without adding DPG to the etching composition in Table 11, and Examples 21 to 23 include DPG in the etching composition in Table 11. It refers to a CuNi / Cu / Ti substrate added by 10, 20, and 30% by weight, respectively, and subjected to an etching test. The results showed that by adding DPG, JET, S / E, and T / A can be controlled, and the smoothness of the resist pattern edge and cross-sectional shape can be improved. Moreover, the SEM photograph of Comparative Example 7 is shown in FIGS. 8 and 14, and the SEM photograph of Example 23 is shown in FIG.

  In Comparative Example 8, when the etching composition shown in Table 11 was prepared, an etching composition in which phosphoric acid was not mixed (that is, (A) hydrogen peroxide, (B) ammonium acid fluoride, (C) nitric acid, (D) Etching composition in which 5-amino-1H-tetrazole (ATZ), (E) tetramethylammonium hydroxide (TMAH), (G) phenylurea and water are mixed) is prepared separately. It refers to a CuNi / Cu / Ti substrate subjected to an etching test without adding DPG. From the results of Comparative Example 7 and Comparative Example 8, it was shown that in the absence of phosphoric acid, in-plane uniformity was greatly reduced, S / E was increased, and the smoothness and cross-sectional shape of the end portion were deteriorated. This is presumed to be caused by the addition of phenylurea. However, when DPG, which is a water-soluble organic solvent, is further added to the component obtained by adding phosphoric acid to the component, that is, the etching composition of Table 11, S / E and T / A can be easily controlled, and the resist pattern edge It was shown that the smoothness and cross-sectional shape of the part can be greatly improved. From this, it was speculated that the water-soluble organic solvent has the effect of further improving the effect of phosphoric acid.

100% O.D. E. Table 13 summarizes the results of the CuNi / Cu / Ti substrates treated with the above. Comparative Example 9 refers to a CuNi / Cu / Ti substrate subjected to an etching test without adding DPG to the etching composition of Table 11, and Examples 24-26 include DPG in the etching composition of Table 11. It refers to a CuNi / Cu / Ti substrate added by 10, 20, and 30% by weight, respectively, and subjected to an etching test. The results showed that by adding DPG, JET, S / E, and T / A can be controlled, and the smoothness of the resist pattern edge and cross-sectional shape can be improved.

50% O.D. E. Table 14 summarizes the results of the Cu / Ti substrates treated with the above. In addition, Comparative Example 10 refers to a Cu / Ti substrate subjected to an etching test without adding DPG to the etching composition of Table 11, and Examples 27 to 29 include DPG in the etching composition of Table 11 and 10 respectively. , 20, and 30% by weight, and refers to a Cu / Ti substrate subjected to an etching test. The results showed that JET, S / E, and T / A can be controlled by adding DPG. In each of the examples, the Ti residue was good, the smoothness of the resist pattern edge was not uneven, and the cross-sectional shape was good.

  In Comparative Example 11, when the etching composition shown in Table 11 was prepared, an etching composition in which phosphoric acid was not mixed (that is, (A) hydrogen peroxide, (B) ammonium acid fluoride, (C) nitric acid, (D) Etching composition in which 5-amino-1H-tetrazole (ATZ), (E) tetramethylammonium hydroxide (TMAH), (G) phenylurea and water are mixed) is prepared separately. It refers to a Cu / Ti substrate subjected to an etching test without adding DPG. From the results of Comparative Example 10 and Comparative Example 11, it was shown that since the phosphoric acid was not contained, the resist pattern edge and the cross-sectional shape were deteriorated. This is presumed to be caused by the addition of phenylurea as described above. However, when DPG, which is a water-soluble organic solvent, is further added to the component obtained by adding phosphoric acid to the component, that is, the etching composition of Table 11, S / E and T / A can be easily controlled, and the resist pattern edge It was shown that the smoothness and cross-sectional shape of the part can be greatly improved. From this, it was speculated that the water-soluble organic solvent has the effect of further improving the effect of phosphoric acid as described above.

50% O.D. E. Table 15 summarizes the results of the Cu / Mo substrates treated with the above. In addition, Comparative Example 12 refers to a Cu / Mo substrate subjected to an etching test without adding DPG to the etching composition of Table 11, and Examples 30 to 32 include DPG in the etching composition of Table 11 and 10 respectively. , 20, and 30% by weight, and refers to a Cu / Mo substrate subjected to an etching test. The results show that JET and T / A can be controlled by adding DPG.

2-5. Etching test by addition of water-soluble organic solvent (A) Hydrogen peroxide, (C) Nitric acid, (D) 5-Amino-1H-tetrazole (ATZ), (E) Tetramethylammonium hydroxide (TMAH), (F) Phosphorus An etching test was conducted with and without adding DPG to an etching composition (Table 16) in which acid, (G) phenylurea and water were mixed. An etching test was performed using a Cu / Ti substrate. O. E. The etching test was conducted under the same test conditions as above.

  The results for the Cu / Ti substrate are summarized in Table 17. Comparative Example 13 refers to a Cu / Ti substrate subjected to an etching test without adding DPG to the etching composition of Table 16, and Example 33 adds 30% by weight of DPG to the etching composition of Table 16. This refers to a Cu / Ti substrate subjected to an etching test. The results show that by adding DPG, JET, S / E, and T / A can be controlled, the disappearance of the resist pattern can be suppressed, the resist pattern edge can be smoothed, and the cross-sectional shape can be made forward tapered. . Thereby, it was confirmed that the Cu single layer film also has the effect of adding the water-soluble organic solvent.

As described above, Mo and Ti are generally used as the barrier metal used in the Cu laminated film, but depending on the application, Ta, other metals, or several metals are used. An alloy or the like may be used. In such a case, it has been shown that if the etching composition of the present invention is used, it is possible to selectively etch only a single layer film of Cu with respect to the laminated film. In this regard, the barrier metal layer may be combined with other etching compositions as long as selective etching that dissolves only Cu is possible like the etching composition of the present invention, such as when processing with other etching compositions. It was suggested that two-stage etching with two liquids was performed, whereby the laminated film could be processed to S / E or T / A within a specified range. When etching a substrate containing titanium at once, it can be performed with an etching composition containing fluorine or a fluorine compound, whereas when selectively etching a substrate containing titanium, fluorine or a fluorine compound is used. It has been shown that this can be done with an etching composition that does not contain.

2-6. Etching test with additive addition (A) Hydrogen peroxide, (B) acidic ammonium fluoride, (C) nitric acid, (D) 5-amino-1H-tetrazole (ATZ) and water mixed etching composition (Table 18) ), (A) hydrogen peroxide, (B) acidic ammonium fluoride, (C) nitric acid, (D) 5-amino-1H-tetrazole (ATZ), (H) DPG and water, Table 19) was subjected to an etching test with and without an additive. An etching test was performed using a Cu / Ti substrate and a Cu / Mo substrate. O. E. The etching test was conducted under the same test conditions as above. The malonic acid used as an additive was added for buffering the solution and improving the solubility of Cu and Mo, and tetramethylammonium hydroxide (TMAH) was used for pH control.

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 compositions shown in Table 18 in increments of 0/2, 2/2, 2/3, 2/4, and 2/5% by weight, respectively. It refers to the provided Cu / Ti substrate (Table 20). Examples 34 to 36 indicate Cu / Ti substrates subjected to an etching test by adding 0/0, 2/2, 2/3, and wt% of malonic acid / TMAH to the etching composition of Table 19, respectively ( Table 21). The results showed that the smoothness at the edge of the resist pattern was improved by adding DPG. When the pH is 5 or more, the solubility of Ti is greatly reduced, and therefore it is shown that the Cu / Ti substrate is preferably pH 4 or less.

The results of the Cu / Mo substrate are summarized in Tables 22 and 23. In Comparative Examples 19 to 24, 0/2, 2/2, 2/3, 2/4, 2/5, and 2/6% by weight of malonic acid / TMAH were added to the etching compositions shown in Table 18, respectively. This refers to the Cu / Mo substrate subjected to the etching test (Table 22). Examples 37 to 39 and Malonic acid / TMAH were added to the etching compositions of Tables 19 and 2/2, 2/3, and 2/4% by weight, respectively, to indicate Cu / Mo substrates subjected to an etching test (Table 23). ). The results show that the composition to which DPG is added suppresses undercutting of Mo, so that the pH range is wider than the composition to which DPG is not added, and the effect of improving S / E and cross-sectional shape is large. From Table 23, it was recognized that Mo undercut does not occur at pH 4 or lower. However, from Table 22 and Table 23, when compared with the composition at pH 4, the substrate etched with DPG has a very small S / E compared to the substrate without addition, so the pH can be adjusted by adjusting the composition ratio. However, it was shown that Mo undercut can be suppressed even with compositions such as pH 5 and pH 6. In addition, since there exists a concern about decomposition | disassembly acceleration | stimulation of hydrogen peroxide at pH 7 or more, less than pH 7 is estimated that the pH of a composition is effective. Moreover, the SEM photograph of the comparative example 21 is shown in FIG. 7, and the SEM photograph of the comparative example 22 is shown in FIG.

  Next, in Comparative Examples 25 to 30 shown below, when preparing the etching composition of Table 18, an etching composition not mixed with acidic ammonium fluoride (that is, (A) hydrogen peroxide, (C) nitric acid, (D) Etching composition in which 5-amino-1H-tetrazole (ATZ) and water are mixed) is prepared separately, and malonic acid / TMAH is added to the etching composition in 0/2, 2/2, 2 and 2, respectively. / 3, 2/4, 2 / 4.5, 2 / 5.5% by weight, and refers to a Cu / Mo substrate subjected to an etching test (Table 24). As for the results of Comparative Examples 25 to 30, relatively good cross-sectional shapes were obtained only at pH 2 to pH 3, but at other pH, Cu or Mo did not dissolve or Mo undercut occurred. Moreover, compared with Comparative Examples 19 to 24 treated with an etching composition containing acidic ammonium fluoride, acidic ammonium fluoride has an effect of suppressing undercutting of Mo and is a water-soluble organic solvent. It was shown that the effect of suppressing Mo undercut is further improved by adding DPG.

2-7. Etching Test with Dependence on pH (A) Hydrogen peroxide, (B) acidic ammonium fluoride, (C) nitric acid, (D) 5-amino-1H-tetrazole (ATZ) and water mixed etching composition (Table 25) And (A) hydrogen peroxide, (B) acidic ammonium fluoride, (C) nitric acid, (D) 5-amino-1H-tetrazole (ATZ), (H) DPG, and water-mixed etching composition (Table An etching test was conducted in 26). An etching test was performed using a Cu / Ti substrate. O. E. The etching test was conducted under the same test conditions as above. The citric acid used as an additive was added for buffering the solution and improving Cu and Ti solubility, and TMAH was used for pH control.

The results of the Cu / Ti substrate are summarized in Tables 27 and 28. In addition, Comparative Examples 31 to 33 indicate Cu / Ti substrates subjected to an etching test by adding citric acid / TMAH to the etching composition of Table 25 by 10/2, 10/3, and 10/8% by weight, respectively. (Table 27), Examples 40 to 42 are Cu / Ti subjected to an etching test by adding citric acid / TMAH to the etching composition of Table 26 by 10/2, 10/3, and 10/8% by weight, respectively. Refers to the substrate (Table 28). As a result, the S / E increases as the pH increases. However, it was shown that the substrate added with DPG can suppress the increase in S / E more than the substrate not added with DPG. In addition, it was shown that the substrate to which DPG was not added had an uneven resist pattern edge, but the substrate to which DPG was added could smooth the edge.

The results of the Cu / Mo substrate are summarized in Table 29 and Table 30. In Comparative Examples 36 to 39, citric acid / TMAH was added to the etching compositions in Table 25 by 10/2, 10/3, 10/8, and 10/10% by weight, respectively, and Cu / It refers to a Ti substrate (Table 29), and Examples 43 to 46 add citric acid / TMAH to the etching composition of Table 26 by 10/2, 10/3, 10/8, and 10/10% by weight, respectively. It refers to a Cu / Mo substrate subjected to an etching test (Table 30). As a result, Mo undercut occurred in all the substrates treated with the composition of Table 25. However, when compared with S / E, it was shown that S / E progresses greatly as the pH increases in the substrate not added with DPG, whereas S / E is suppressed in the substrate added with DPG. . In addition, it was shown that the substrate to which DPG is not added has an uneven resist pattern edge, but the substrate to which DPG is added can be made smooth. All the substrates in Table 29 have Mo undercut. However, it was suggested that this can be suppressed by adjusting the composition ratio as in the case of using malonic acid. It was also suggested that S / E can be suppressed by adding DPG. As in the case of using malonic acid instead of citric acid, there is a concern that peroxide decomposition may be accelerated at a pH of 7 or higher, and it is estimated that a pH range of less than pH 7 is effective.

2-8. Etching test by addition of water-soluble organic solvent (A) Hydrogen peroxide, (B) Acidic ammonium fluoride, (C) Nitric acid, (D) 5-Amino-1H-tetrazole (ATZ), (E) Tetramethylammonium hydroxide (TMAH), (G) Etching composition mixed with phenylurea and water (Table 31), 2-propanol (IPA), diethylene glycol (DEG), dimethyl sulfoxide (DMSO), 1,3-butanediol (BD) 1,3-dimethyl-2-imidazolidinone (DMI), N-methyl-2-pyrrolidinone (NMP), glycerin (Gly) and N, N-dimethylacetamide (DMAc) are added and not added, respectively. An etching test was performed. An etching test was performed using a CuNi / Cu / Ti substrate. O. E. The etching test was conducted under the same test conditions as above.

Table 32 summarizes the results of etching the CuNi / Cu / Ti substrate using IPA as the water-soluble organic solvent. Comparative Example 40 refers to a CuNi / Cu / Ti substrate subjected to an etching test without adding IPA to the etching composition of Table 31, and Examples 47 to 49 include IPA in the etching composition of Table 31. It refers to a CuNi / Cu / Ti substrate added by 10, 20, and 30% by weight, respectively, and subjected to an etching test. The results show that IPA can also control JET, S / E, and T / A compared to the substrate without addition, smooth the resist pattern edge, and make the cross-sectional shape forward tapered.

Table 33 summarizes the results of etching the CuNi / Cu / Ti substrate using DEG and DMSO as the water-soluble organic solvent. In addition, Examples 50 to 52 indicate CuNi / Cu / Ti substrates subjected to an etching test by adding DEG to the etching composition of Table 31 by 10, 20, and 30% by weight, respectively. The CuNi / Cu / Ti board | substrate which added DMSO to the etching composition of Table 31, respectively by 10, 20, and 30 weight%, respectively, and was used for the etching test. As a result, it was shown that DEG and DMSO can control JET, S / E, and T / A as compared with the substrate not added, smooth the resist pattern end, and make the cross-sectional shape forward tapered.

Table 34 shows the results of etching the CuNi / Cu / Ti substrate using BD and DMI as the water-soluble organic solvent. In addition, Examples 56 to 58 indicate CuNi / Cu / Ti substrates subjected to an etching test by adding BD to the etching composition of Table 31 by 10, 20, and 30% by weight, respectively. Examples 59 to 61 The CuNi / Cu / Ti board | substrate which added DMI to the etching composition of Table 31, respectively by 10, 20, and 30 weight%, respectively, and was used for the etching test. As a result, it was shown that JET, S / E, and T / A can also be controlled for BD and DMI as compared with the substrate not added, the resist pattern edge portion can be smoothed, and the cross-sectional shape can be forward tapered.

Table 35 summarizes the results of etching the CuNi / Cu / Ti substrate using NMP and Gly as the water-soluble organic solvent. Examples 62 to 64 refer to CuNi / Cu / Ti substrates subjected to an etching test by adding NMP to the etching composition of Table 31 by 10, 20, and 30% by weight, respectively. The CuNi / Cu / Ti board | substrate which added Gly to the etching composition of Table 31, respectively by 10, 20, and 30 weight%, respectively, and was used for the etching test. The results show that NMP and Gly can also control JET, S / E, and T / A as compared to the substrate not added, smooth the resist pattern end, and make the cross-sectional shape forward tapered.

Table 36 shows the results of etching the CuNi / Cu / Ti substrate using DMAc as the water-soluble organic solvent. In addition, Examples 68-70 point out the CuNi / Cu / Ti board | substrate which added DMAc to the etching composition of Table 31 by 10, 20, and 30 weight%, respectively, and used for the etching test. As a result, it can be seen that DMAc can also control JET, S / E, and T / A as compared with the substrate not added, smooth the resist pattern end, and make the cross-sectional shape forward tapered.

  From the above results, it was shown that by using a water-soluble organic solvent, JET, S / E, and T / A can be controlled, and the resist pattern end can be smoothed and the cross-sectional shape can be forward tapered.

2-9. Etching test with peroxide (A) Ammonium peroxodisulfate, (B) Ammonium acid fluoride, (C) Nitric acid, (D) 5-amino-1H-tetrazole (ATZ), (G) Phenylurea and water were mixed An etching test was conducted with the etching composition (Table 37). An etching test was performed using a CuNi / Cu / Ti substrate. O. E. The etching test was conducted under the same test conditions as above.

The results for the CuNi / Cu / Ti substrate are summarized in Table 38. Comparative Example 41 refers to a CuNi / Cu / Ti substrate subjected to an etching test without adding DPG to the etching composition of Table 37. Examples 71 and 72 include DPG in the etching composition of Table 37. It refers to a CuNi / Cu / Ti substrate that was added by 10 and 20% by weight and subjected to an etching test. As a result, it was shown that the substrate added with DPG can control JET, S / E, and T / A as compared with the substrate not added with DPG, and the cross-sectional shape can be a forward tapered shape. As a result, peroxides such as ammonium peroxodisulfate can obtain almost the same effect as hydrogen peroxide. Therefore, it was shown that ammonium peroxodisulfate can be substituted for hydrogen peroxide.

3. Liquid life and replenishment test 3-1. Liquid Life Evaluation Test (A) Hydrogen peroxide (B) Hydrofluoric acid, (C) Nitric acid, (D) 5-Amino-1H-tetrazole (ATZ), (E) TMAH, (G) Phenylurea, (H ) A liquid life evaluation test was conducted using an etching composition (Table 39) in which DPG and water were mixed. The liquid life evaluation test is a test for confirming a change in performance when the amount of copper dissolved is increased. Moreover, about melt | dissolution of copper, it melted and tested the copper powder instead of the copper substrate. The substrate subjected to the test was subjected to an etching test using a CuNi / Cu / Ti substrate. O. E. The etching test was conducted under the same test conditions as above.

The results for CuNi / Cu / Ti substrates are summarized in Table 40. In addition, Example 74 points out the CuNi / Cu / Ti board | substrate processed with the etching composition which does not add copper to the etching composition of Table 39, and Examples 75-77 respectively have copper amount to the etching composition of Table 39. Refers to a CuNi / Cu / Ti substrate treated with an etching composition in which 1000, 2000 and 3000 ppm are dissolved. It was shown that the performance of Comparative Examples 75 to 77 treated with an etching composition in which copper was dissolved from 0 ppm to 2000 ppm gradually decreased. Moreover, it was shown that Example 77 treated with an etching composition in which 3000 ppm of copper was dissolved significantly deteriorated in performance and Ti residue was generated. Although not shown in the following table, when copper was added up to 4000 ppm, copper itself was not completely dissolved in the etching composition.

3-2. Liquid life replenishment test Next, the etching composition of Table 39 was mixed with (A) hydrogen peroxide (B) hydrofluoric acid, (C) nitric acid, (D) TMAH and water as a replenisher. A liquid life replenishment test was conducted while adding the composition of (Table 41). In addition, the addition method of the replenisher used what added 1.8 volume% or 2.0 volume% with respect to the volume of the etching composition for every 1000 ppm of copper dissolution amounts as an etching composition. The substrate subjected to the test was subjected to an etching test using a CuNi / Cu / Ti substrate. O. E. The etching test was conducted under the same test conditions as above.

The results for CuNi / Cu / Ti substrates are summarized in Table 42. In addition, Example 78 refers to a CuNi / Cu / Ti substrate treated with an etching composition in which no additional copper powder and replenisher are added to the etching composition of Table 39, and Examples 79 to 82 are etchings of Table 39. An etching composition in which copper powder was added to the composition at 8000, 16000, 24000, and 32000 ppm, respectively, and the replenisher of Table 41 was added at 14.4, 32.0, 46.8, and 62.4% by volume, respectively. It refers to the treated CuNi / Cu / Ti substrate. The results showed that in Example 77, Ti residue was generated at a copper dissolution amount of 3000 ppm, whereas in Example 82, Ti residue was not generated even when 32000 ppm of copper was dissolved. In addition, it was shown that the performance was maintained almost equal to the initial performance. By adding a composition containing peroxide, nitric acid, fluorine and / or fluorine compound, TMAH or a water-soluble organic solvent as a replenisher to the etching composition used in the present invention, the liquid life can be reduced. It was confirmed that it could be extended.

  When etching is performed using the etching composition of the present invention, a single layer film and / or a laminated film can be collectively etched to manufacture a complex and precise substrate, and high productivity can be achieved. In addition, a substrate manufactured by an etching method using the etching composition can be used for a more advanced high-performance flat panel display or the like. Furthermore, by using the replenisher, the life of the liquid is extended, which contributes to the cost reduction of the board production and can further improve the safety.

Claims (20)

  It consists of a metal selected from the group consisting of copper, titanium, molybdenum and nickel or a single layer film consisting of these nitrides, and an alloy containing one or more selected from the group consisting of copper, titanium, molybdenum and nickel An etching composition for etching a single layer film or a laminated film comprising one or more of the single layer films, comprising an azole, nitric acid, peroxide and a water-soluble organic solvent .   The etching composition according to claim 1, wherein the water-soluble organic solvent has a vapor pressure of 2 kPa or less at 25 ° C.   The etching composition according to claim 1 or 2, wherein the water-soluble organic solvent is selected from the group consisting of alcohol, glycol, diol, triol, ketone, carbonate, and sulfoxide.   The etching composition 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 dipropylene glycol.   The etching composition according to any one of claims 1 to 4, wherein the peroxide is selected from the group consisting of hydrogen peroxide, ammonium peroxosulfate, sodium peroxosulfate and potassium peroxosulfate.   The etching composition as described in any one of Claims 1-5 which further contains phosphoric acid or a phosphate.   The etching composition according to any one of claims 1 to 6, further comprising a compound selected from the group consisting of quaternary ammonium hydroxide and aqueous ammonia.   The etching composition according to claim 1, further comprising fluorine or a fluorine compound.   The etching composition according to claim 8, wherein the fluorine compound is selected from the group consisting of ammonium fluoride, ammonium acid fluoride and hydrofluoric acid.   The etching composition according to any one of claims 1 to 9, further comprising a urea compound.   11. The etching composition according to claim 10, wherein the urea compound is selected from the group consisting of phenylurea, allylurea, 1,3-dimethylurea and thiourea.   The etching composition according to claim 1, further comprising an organic acid.   The etching composition according to claim 12, wherein the organic acid is malonic acid or citric acid.   1 to 15% by mass of peroxide, 1 to 10% by mass of nitric acid, 0.005 to 0.2% by mass of azoles, 0.05 to 1.00% by mass of fluorine compound, 1 to 50% by mass of The etching composition as described in any one of Claims 1-13 containing a water-soluble organic solvent.   It is an etching composition for etching a laminated film, Comprising: The laminated film consists of a layer structure of titanium / copper / titanium, The etching composition as described in any one of Claims 1-14.   The etching composition for etching a laminated film, wherein the laminated film has a layer structure of an alloy composed of copper and nickel / copper / titanium, and the titanium is on the substrate side. The etching composition according to one item.   15. 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, and the single layer of molybdenum is on the substrate side. The etching composition as described in any one of these.   The etching composition according to any one of claims 1 to 17, wherein the pH is less than 7.0.   It consists of a metal selected from the group consisting of copper, titanium, molybdenum and nickel or a single layer film consisting of these nitrides, and an alloy containing one or more selected from the group consisting of copper, titanium, molybdenum and nickel A method for etching a single layer film or a laminated film comprising one or more of the single layer films, the step of etching using the etching composition according to claim 1. Said method.   The method of Claim 19 used for the manufacturing process or packaging process of a liquid crystal display, a color film, a touch panel, an organic electroluminescent display, electronic paper, MEMS, or IC.