TW201809357A - Etching composition for single layer film or multiple layer film and etching method using the same - Google Patents

Abstract

The present invention is to provide an etching composition for etching metal single layer film or metal multiple layer film. Compared to prior art, the present invention can achieve an optimal etching rate and easily control side etching, coning angle, cross-section shape, and pattern shape, so as to maintaim stable property and prolong the service life of a replenishing liquid. The etching composition of the present invention is used to etch the following single layer film or multiple layer film, in which the single film is formed of a metal selected from a group of copper, titanium, molybdenum and nickel, or a nitride selected from the group of metals, or an alloy containing one or two selected from the group of metals. The multiple layer film includes one or two of the single layer film. The etching composition includes azole, nitric acid, peroxide and water-soluble organic solvent.

Description

Etching composition of single-layer film or laminated film and etching method using the same

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 and the like, and an etching method using the same.

As a wiring material for a display device such as a flat panel display, copper or an alloy containing copper is used as a material having low resistance. However, copper originally has insufficient adhesion to a substrate such as glass, and copper also has a property of diffusing into a silicon semiconductor film. Therefore, recently, it has been known that a barrier metal layer such as a titanium layer or a molybdenum layer is provided as a barrier film between a substrate and a wiring material such as a copper layer to improve the adhesion between the wiring material and the glass substrate and prevent diffusion to the silicon semiconductor film. Furthermore, in order to prevent oxidation of the copper layer and the like, a three-layer build-up film in which a cap film is formed on the upper layer of the copper layer also exists.

As an etching solution for a copper and titanium laminated film, for example, the following etching has been proposed Liquid: Etching solution containing hydrogen peroxide, nitric acid, fluoride ion supply source, azoles, quaternary ammonium hydroxide, hydrogen peroxide stabilizer, and water at a pH of 1.5 to 2.5 (Patent Document 1); containing ammonium persulfate , Organic acid, ammonium salt, fluorinated compound, powder of glycol-based compound, azole-based compound, and water (Patent Document 2); etchant containing ammonium persulfate, azole-based compound, and water (Patent Document 3) ; An etching solution containing a fluoride ion supply source, hydrogen peroxide, sulfate, phosphate, azole-based compound, and water (Patent Document 4).

In addition, as an etching solution for a copper and molybdenum multilayer film, for example, the following etching solution has been proposed: 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); an etching solution containing hydrogen peroxide, a non-fluorine-containing inorganic acid, an amine compound, an azole, and a hydrogen peroxide stabilizer (Patent Document 6); an aqueous medium containing ammonia and a compound having an amine group , A composition for etching with hydrogen peroxide and a pH exceeding 8.5 (Patent Document 7) and the like.

[Prior technical literature] [Patent Literature]

Patent Document 1: Japanese Patent No. 5685204.

Patent Document 2: Japanese Patent Application Laid-Open No. 2013-522901.

Patent Document 3: Japanese Patent Application Laid-Open No. 2008-227508.

Patent Document 4: Japanese Patent Application Laid-Open No. 2008-288575.

Patent Document 5: Japanese Patent No. 4282927.

Patent Document 6: International Publication No. 2011/099624.

Patent Document 7: Japanese Patent Application Laid-Open No. 2010-232486.

Regarding the etching solutions described in Patent Document 1, Patent Document 4 to Patent Document 7, there are cases where the in-plane uniformity is insufficient and a large number of irregularities are generated at the ends of the resist pattern. If the corrosion further progresses, This may result in a mouse bite that is shaped like a trace left by a mouse biting on cheese, thereby reducing the yield, or causing the cross-sectional shape to be rough and uneven. In addition, the composition for etching described in the cited document 7 has problems in terms of usability such as short liquid life and low storage stability. In addition, as for the etching solutions described in Patent Documents 2 and 3, persulfate is used, but when persulfate is used, the end portions of the resist pattern are more likely to be uneven than hydrogen peroxide. In addition, there is a problem that the taper angle is difficult to control and easily becomes low.

Therefore, the object of the present invention is to provide an etching composition for solving the above-mentioned problems, which can be used to etch a metal single-layer film or a metal multilayer film, and can achieve an excellent etching rate, and easily control side etching, taper angle, and section Shape, pattern shape, and thus maintain performance stability and have longer liquid life.

The present inventors conducted intensive research in order to solve the above-mentioned problems. In the process, they focused on phenylurea or phenolsulfonic acid used as a stabilizer for peroxides, and malonic acid to increase the amount of dissolved copper. Organic acids or chelants, Studies have been conducted to obtain a buffering effect of pH, such as neutral salts, as the main cause of the decrease in in-plane uniformity. As a result, it was found that the etching created by mixing a peroxide-containing etching composition with a water-soluble organic solvent The composition can improve the wettability to the metal substrate, smoothly etch the metal surface, suppress local corrosion, and further study, and as a result, completed the present invention.

That is, the present invention relates to the following.

[1] An etching composition for etching the following single-layer film or laminated film, the single-layer film is a metal selected from the group consisting of copper, titanium, molybdenum, and nickel or a nitride of these metals Or is composed of an alloy containing one or two or more alloys selected from the group consisting of copper, titanium, molybdenum, and nickel, and the laminated film includes the single-layer film of one or more layers, and The etching composition includes azole, nitric acid, peroxide, and a water-soluble organic solvent.

[2] The etching composition according to the above [1], wherein a water pressure of the water-soluble organic solvent at 25 ° C. is 2 kPa or less.

[3] The etching composition according to the above [1] or [2], wherein the water-soluble organic solvent is selected from the group consisting of alcohol, glycol, glycol, triol, ketone, carbonate, and sulfonium.

[4] The etching composition according to any one of the aforementioned [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 the above [1] to [4], wherein The middle peroxide is selected from the group consisting of hydrogen peroxide, ammonium persulfate, sodium persulfate, and potassium persulfate.

[6] The etching composition according to any one of the above [1] to [5], further comprising phosphoric acid or a phosphate.

[7] The etching composition according to any one of the above [1] to [6], further comprising a compound selected from the group consisting of a quaternary ammonium hydroxide and ammonia water.

[8] The etching composition according to any one of the above [1] to [7], further comprising 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, acid ammonium fluoride, and hydrofluoric acid.

[10] The etching composition according to any one of the above [1] to [9], further comprising a urea compound.

[11] The etching composition according to the aforementioned [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 the above [1] to [11], further comprising an organic acid.

[13] The etching composition according to [12], wherein the organic acid is malonic acid or citric acid.

[14] The etching composition according to any one of the above [1] to [13], which contains 1% to 15% by mass of a peroxide, 1% by mass Nitric acid to 10% by mass, azoles from 0.005% to 0.2% by mass, fluorine compounds from 0.05% to 1.00% by mass, and water-soluble organic solvents from 1% to 50% by mass.

[15] The etching composition according to any one of [1] to [14], used to etch a laminated film, and the laminated film is composed of a titanium / copper / titanium layer.

[16] The etching composition according to any one of [1] to [14], used to etch a laminated film, and the laminated film is composed of an alloy / copper / titanium layer composed of copper and nickel, The aforementioned titanium is located on the substrate side.

[17] The etching composition according to any one of the above [1] to [14], used to etch a laminated film, and the laminated films are each a single layer of copper / a single layer of molybdenum, the foregoing A single layer of molybdenum is located on the substrate side.

[18] The etching composition according to any one of the above [1] to [17], wherein the pH does not reach 7.0.

[19] A method for etching the following single-layer film or laminated film, which is composed of a metal selected from the group consisting of copper, titanium, molybdenum, and nickel, or a nitride of these metals, or Containing one or two or more alloys selected from the group consisting of copper, titanium, molybdenum, and nickel, the laminated film comprises one or two or more of the foregoing single-layer films, and the method includes using, for example, The etching step of the etching composition according to any one of the above [1] to [18].

[20] The method according to the aforementioned [19], which is used for liquid crystal displays, color films, touch panels, and organic EL (electroluminescence; Manufacturing steps or packaging steps of a light) display, electronic paper, MEMS (Micro-Electro-Mechanical System) or IC (integrated circuit).

The etching composition of the present invention has improved wettability to metals due to the organic solvent contained in the etching composition, and can etch a single-layer film and / or a multi-layer film at one time. In addition, it can not only improve the etching rate, but also easily control the side etching and taper angle, and the in-plane uniformity is high. It can realize the smooth etching of the resist end or cross-sectional shape, and it can etch complex and delicate substrates. In addition, the etching composition has excellent stability and can be used for a long time. In addition, by supplementing the etching composition with a replenishing solution containing one or two or more components of the etching composition of the present invention, the performance can be maintained and the life of the liquid can be prolonged. Therefore, it can also contribute to reduction of manufacturing cost and safety during substrate manufacturing.

In particular, undercuts of titanium and molybdenum that were previously easily generated in a multilayer film containing copper and titanium or a multilayer film containing copper and molybdenum can be easily suppressed. In addition, when a titanium layer or a molybdenum layer with a film thickness of about 100 nm is present in the upper layer, it also has the effect of preventing extreme etching near the interface of the upper layer. The single-layer film also has the effect of preventing the smoothness of the ends of the resist pattern or the deterioration of the cross-sectional shape. In addition, even if a peroxide stabilizer or an organic acid or a chelating agent is added, and no stabilizer or a pH buffer is added, it may cause a decrease in in-plane uniformity or cause rodents at the ends of the resist pattern. efficacy.

FIG. 1 is a schematic cross-sectional view of an etched Cu / Ti substrate.

FIG. 2 is a schematic diagram of a cross-section of a Cu / Mo substrate that produces an Mo undercut.

FIG. 3 is a schematic view of a cross section of a CuNi / Cu / Ti substrate in which a copper alloy has a brim shape.

FIG. 4 is a schematic cross-sectional view of a Ti substrate subjected to etching treatment.

FIG. 5 is a schematic cross-sectional view of a Ti substrate whose upper layer portion is extremely etched.

FIG. 6 is a SEM (Scanning Electron Microscope) image of a cross-section of a forward-tapered Cu / Ti substrate.

FIG. 7 is a SEM photograph of a cross section of a Cu / Mo substrate with a Mo undercut in the cross section.

FIG. 8 is a SEM photograph of a cross-section of a CuNi / Cu / Ti substrate in which the upper layer portion of the cross-section has a brim shape.

FIG. 9 is a SEM photograph of a cross section of a Ti substrate having a forward tapered shape.

FIG. 10 is a SEM photograph of a Ti substrate.

11 is a schematic diagram of a cross-sectional shape of an end portion of a resist pattern obtained by obliquely observing an etched CuNi / Cu / Ti substrate.

FIG. 12 is a schematic view of a cross-sectional shape obtained by obliquely observing a CuNi / Cu / Ti substrate whose edges of the resist pattern are roughened and uneven.

FIG. 13 is an SEM photograph of a cross-sectional shape of a resist pattern end portion obtained by obliquely observing an etched CuNi / Cu / Ti substrate.

FIG. 14 is an SEM photograph of a cross-sectional shape obtained by obliquely observing a CuNi / Cu / Ti substrate whose end portion of the resist pattern is roughened into an uneven shape.

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

In this specification, for example, Cu / Ti, CuNi / Cu / Ti, etc. may be used. Cu / Ti indicates a two-layer film of copper and titanium, CuNi / Cu / Ti indicates an alloy of copper and nickel, and three layers of copper and titanium. membrane. Regarding the order of the layers, Cu / Ti indicates that copper is laminated on top of titanium, CuNi / Cu / Ti indicates an alloy of copper laminated on top of titanium, and nickel is stacked on copper. Therefore, for any of the above-mentioned laminated films, the layer closest to the substrate surface means a layer of titanium.

The etching composition of the present invention is formed on a single-layer film and / or a laminated film on a substrate, coated with a resist, exposed and transferred a desired pattern mask, and developed to form a resist pattern. After that, the single-layer film and / or the multilayer film are etched, and finally a wiring or an electrode pattern is formed on the substrate. In this respect, as shown in FIG. 1, regarding the performance required for etching, it is preferable that the angle (taper angle) formed by the etching surface of the copper wiring end and the underlying substrate is less than 90 ° in the shape of a positive cone. , More preferably 20 ° to 60 °. especially, In the case of a copper-free barrier metal layer, such as a single-layer film such as Ti or Mo, because the film thickness is thin, even if it is a high angle of 70 ° or 80 °, there is actually no special problem on the substrate, so it is used as Positive cone shape is included in the preferred range.

In addition, the distance from the end of the resist to the barrier film provided under the wiring (side etch) is preferably within about three times the film thickness of the laminated film. It is more preferably within about 1.5 times. For example, if the film thickness of Cu / Ti is 0.6 μm (6000 Å), it is preferably within 2.0 μm, and more preferably within 0.9 μm. Further, as shown in FIG. 2, a state where the barrier metal layer under the copper layer is etched is called a so-called barrier metal undercut. In this state, the undercut portion becomes a hole and becomes a disconnected state, so it cannot be used as a substrate. . Therefore, it is not good as an etching.

In addition, as shown in FIG. 3, when the three-layer build-up film on which the cap film is formed on the copper layer is etched, when the metal of the cap film is harder to dissolve than copper, it becomes a brim shape. The brim-shaped state is also called an inverted cone, and it is in a disconnected state as described above, so it cannot be used as a substrate, so it is not good for etching. A better etching state of the single layer is shown in the cross-sectional view of the Ti substrate shown in FIG. 4. That is, the taper has a forward taper shape with a taper angle of 20 ° to 60 °, and the side etch is 0.9 μm or less. In addition, a schematic view of the cross section of the Ti substrate shown in FIG. 5 shows a state when the etchant enters the interface between the resist and Ti. The Ti upper layer portion is in a state of being extremely etched, and of course, it is not a preferable state. In addition, FIG. 10 is a SEM photograph of a Ti substrate treated with a general etching composition including hydrogen peroxide, ammonia, and phosphate. Ti upper layer It is in a state of being extremely etched, which is not a preferable state.

Furthermore, FIG. 11 and FIG. 12 show the shape of the resist pattern end portion when viewed obliquely from above. FIG. 11 shows a state where the smoothness is high in the etching rear end portion, and FIG. 12 shows a state where the smoothness is low. In addition, it is preferable that the etching rear end portion has high smoothness. That is, the etching composition preferably satisfies the above-mentioned conditions.

The etching target of the etching composition of the present invention is a single-layer film or a multilayer film of a metal formed on a glass or a silicon substrate. Furthermore, it may be a multilayer film including one layer or two or more layers of a single-layer film composed of the above-mentioned metal or alloy.

In one aspect of the present invention, the single-layer film or the multilayer film includes a nitride of a metal selected from the group consisting of copper, titanium, molybdenum, and nickel. A single-layer film of TiN or MoN or a multilayer film containing these is preferred.

The titanium alloy or molybdenum alloy used in the single-layer film or the laminated film has titanium or molybdenum as the main component, but of course, it can also contain other metals such as aluminum, magnesium, and calcium. Furthermore, the titanium alloy or molybdenum alloy contains 80% by weight or more of titanium or molybdenum with respect to the alloy weight, preferably 90% by weight or more, and more preferably 95% by weight or more.

The laminated film may be any of two layers, three layers, four layers, and five layers, but it is preferably two layers and three layers. Examples of the two-layer laminated film include Cu / Ti, Cu / MoTi, Cu / TiN, Cu / Mo, Cu / MoN, and the like are not limited to these. It can also be a laminated film formed by forming a barrier metal from Ti or Mo or an alloy layer of these, and further forming a Cu or Cu alloy film on the barrier metal.

Examples of the three-layer laminated film include: 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 are not limited to these. When an oxide semiconductor such as IGZO (indium gallium zinc oxide) is used for the channel layer, the Cu electrode is exposed to an oxygen atmosphere. Therefore, Ti, Mo, or an alloy of these is used for protection in most cases. membrane. However, if these films are formed on the copper upper layer portion, it is difficult to process with one solution or make the cross-sectional shape uniform. Therefore, a copper alloy such as CuNi or CuMgAl is used as the cap film.

In particular, a multilayer film including a copper layer and a molybdenum layer is mostly used for wiring of display devices such as flat panel displays. The etching composition of the present invention is suitable for the multilayer film. In addition, in many cases, a film formed of an electrode or a wiring is made of an alloy of titanium, molybdenum, nickel, or the like as a barrier metal and is used for a single-layer film. In order to suppress diffusion to silicon or the like, in most cases, the barrier is also used as described above. Copper or copper alloys are formed on the metal. The etching composition of the present invention is not only suitable for blocking a single-layer film of metal, but also suitable for blocking selective etching of a copper or copper alloy film on a metal.

In addition, TFT (Thin Film Transistor) is used to control light by the liquid crystal of the flat panel display. There are a gate electrode and a source electrode / drain electrode on the TFT. The gate electrode is located at the lowest layer of the TFT, and the source electrode / drain electrode is located at the upper layer. In terms of electrical characteristics, the gate electrode is usually set to have a thicker film such as Cu / Ti or Cu / Mo. In contrast, the source electrode / drain electrode is sometimes set to be thin. For example, the copper of the gate electrode is 6000Å, and the copper of the source electrode / drain electrode is 3000Å, but it is not limited to this. Therefore, it is preferable to prepare the etching composition of the present invention in a manner that can cope with any film thickness.

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

The etching composition of the present invention contains a water-soluble organic solvent. The water-soluble organic solvent helps to control the etching rate, side etching, cone angle, etc., smooth the ends of the resist pattern, and control the cross-sectional shape. The water-soluble organic solvent used in the etching composition of the present invention is preferably a liquid compatible with water, more preferably a water-soluble organic solvent having a vapor pressure of 25 kPa or lower at 25 ° C and compatible with water. Furthermore, water-soluble organic solvents which are solid at normal temperature are excluded. In particular, alcohols, glycols, triols, ketones, amidines, nitrogen-containing five-membered rings, carbonates, and sulfoniums are more preferred. Furthermore, of course One or two or more of these water-soluble organic solvents are 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, 1-butanol, or a glycol such as ethylene glycol, propylene glycol, or butanediol. . In particular, propanol, 2-propanol, and 1-butanol are preferred, and propanol and 2-propanol are more preferred.

The glycol used in the etching composition of the present invention is preferably diethylene glycol, dipropylene glycol, 1,3-propanediol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol Glycol, 1,5-pentanediol, etc. Particularly, diethylene glycol, dipropylene glycol, 1,3-propanediol, 1,3-butanediol, 2,3-butanediol, and 1,4-butanediol are more preferable, and diethylene glycol is particularly preferable. Alcohol, dipropylene glycol, 1,3-butanediol.

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

The ketone used in the etching composition of the present invention is preferably acetone, ethylmethyl ketone, diethyl ketone, methylpropyl ketone, ethylpropyl ketone, dipropyl ketone, or the like. In particular, acetone is more preferable.

The amidine 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-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidone, or the like. In particular, 1,3-dimethyl-2-imidazolidinone and N-methyl-2-pyrrolidone are more preferable.

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

Examples of the fluorene used in the etching composition of the present invention include dimethyl fluorene and the like, and dimethyl fluorene is preferred.

Regarding the content of the water-soluble organic solvent in the etching composition of the present invention, it is preferable in terms of appropriately ensuring control of the etching rate, side etching, taper angle, etc., smoothing the ends of the resist pattern, and controlling the cross-sectional shape. It is 1 to 50% by mass, and more preferably 5 to 30% by mass.

The etching composition of the present invention contains one kind or two or more kinds of peroxides. Peroxide has the function of oxidizing copper wiring as an oxidant. In particular, it has the function of oxidizing and dissolving molybdenum. The peroxide is preferably hydrogen peroxide, ammonium peroxodisulfate, ammonium peroxodisulfate, sodium peroxodisulfate, potassium persulfate, and more preferably hydrogen peroxide or ammonium peroxodisulfate. It is preferable that the content of peroxide in the etching composition of the present invention is such that the amount of peroxide in the etching composition of the present invention can be easily controlled and hydrogen etching can be ensured at a moderate etching rate. 1% to 15% by mass, and more preferably 3% to 6% by mass.

The etching composition of the present invention contains nitric acid. Nitric acid helps dissolve copper and the like oxidized by peroxide. The content of nitric acid in the etching composition of the present invention is preferably from 1% by mass to 10% by mass, and more preferably from 2% by mass to the point that a moderate etching rate is obtained and a good wiring shape after etching is obtained. 7% by mass.

The etching composition of the present invention contains one or more azoles. The azole helps control side erosion, cone angle, and cross-sectional shape. The azole used in the etching composition of the present invention is preferably 1,2,4-1H-triazole, 1H-benzotriazole, 5-methyl-1H-benzotriazole, 3-amino-1H- Triazoles and triazoles such as 3-amino-1H-1,2,4-triazole, 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole and 5-amine Tetrazole such as 1H-tetrazole, imidazole such as 1H-imidazole and 1H-benzimidazole, and thiazole such as 1,3-thiazole and 4-methylthiazole. In particular, triazole and tetrazole are more preferred, and 1,2,4-1H-triazole, 3-amino-1H-1,2,4-triazole and 5-amino-1H-tetrazol are more preferred. Aminotetrazole (ATZ).

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

The etching composition of the present invention may further include one or two or more kinds. Phosphoric acid (phosphate) or phosphorus oxide. Phosphate ions obtained from phosphoric acid (phosphate) or phosphorus oxy compounds help control the etching rate of copper, titanium, molybdenum, nickel, or alloys of these or control the taper angle. From the viewpoint of easily controlling the etching rate or the taper angle, the content of phosphoric acid (phosphate) or phosphorus oxide compound further contained in the etching composition of the present invention is preferably from 0.1% by mass to 30.0% by mass, and more preferably 1.0% by mass. % To 4.0% by mass.

The phosphate ion is not particularly limited as long as it generates phosphate ion in the etching composition, and is preferably phosphoric acid (phosphate), ammonium dihydrogen phosphate, diammonium hydrogen phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, and phosphoric acid. Magnesium monohydrogen, magnesium dihydrogen phosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, calcium monohydrogen phosphate, calcium dihydrogen phosphate, and the like. Of course, these can be used individually or in combination. In particular, phosphoric acid (phosphate) is more preferable because it is easy to handle because of liquid.

The etching composition of the present invention may further contain one or more basic compounds. Basic compounds help control pH, improve wettability to fine parts, and improve in-plane uniformity. The basic compound is preferably a quaternary ammonium hydroxide, ammonia or hydroxide, more preferably a tetramethylammonium hydroxide, a tetraethylammonium hydroxide, and a trimethyl (2-hydroxyethyl) ammonium hydrogen. Alkali hydroxides such as oxides, lithium hydroxide, sodium hydroxide, and potassium hydroxide; alkaline earth hydroxides such as calcium hydroxide, strontium hydroxide, and barium hydroxide; ammonium carbonate, lithium carbonate, sodium carbonate, and potassium carbonate Carbonates such as alkali metals, quaternary ammonium hydroxides such as tetramethylammonium hydroxide and choline, organic amines such as ethylamine, diethylamine, triethylamine, and hydroxyethylamine, and ammonia. Especially Tetramethyl ammonium hydroxide (TMAH) is preferred.

In terms of obtaining a good cross-sectional shape of the wiring after the etching, the content of the basic compound in the etching composition of the present invention is preferably 1% by mass to 20% by mass, and more preferably 1% by mass to 7% by mass.

The etching composition of the present invention may further contain one or more fluorine or fluorine compounds. The fluorine ions obtained from fluorine or a fluorine compound are particularly useful for etching of a barrier film composed of a titanium-based metal. The fluorine ion is not particularly limited as long as it generates fluorine ion in the etching composition, and it is preferably hydrofluoric acid, ammonium fluoride, acid ammonium fluoride, or the like. Of course, the above-mentioned substances may be used alone or in combination. Particularly, in terms of low toxicity to animals, ammonium fluoride, acid ammonium fluoride, and hydrofluoric acid are more preferable.

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

The etching composition of the present invention may further contain one or two or more urea-based hydrogen peroxide stabilizers. Urea-based hydrogen peroxide stabilizers help to suppress the decomposition of peroxides. The urea-based hydrogen peroxide stabilizer is preferably phenylurea, allylurea, 1,3-dimethylurea, thiourea, and the like, and particularly preferably phenylurea. The content of the urea-based hydrogen peroxide stabilizer in the etching composition of the present invention is preferably from 0.1% by mass to 2.0% by mass, and from the viewpoint that the effect of suppressing the decomposition of hydrogen peroxide is appropriately obtained, it is more preferably 0.1% by mass. % To 0.3% by mass.

The etching composition of the present invention may further contain one or more organic acids. The organic acid functions as a buffer for adjusting the pH in the etching composition. Organic acids are preferably ammonium salts, citric acid, sodium citrate, sodium dihydrogen citrate, disodium 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 (for example, sodium tartrate, sodium hydrogen tartrate, and potassium potassium tartrate), tris (hydroxymethyl) aminomethane (Tris) and its salts (for example, tris (hydroxymethyl) aminomethane hydrochloride) , Malonic acid, triammonium citrate, diammonium citrate, ammonium lactate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, and the like. In particular, citric acid, malonic acid, diammonium hydrogen phosphate, and ammonium dihydrogen phosphate are more preferred.

In addition to the above-mentioned components, the etching composition of the present invention may further include one or two or more kinds of various additives generally used in other etching compositions to the extent that the efficacy of the etching composition is not impaired. Water is better to borrow Removal of metal ions or organic impurities, particulates, etc. by distillation, ion exchange treatment, filter treatment, various adsorption treatments, etc., especially pure water and ultrapure water.

In a preferred aspect of the etching composition of the present invention, the etching composition of the present invention preferably includes a peroxide, fluorine or a fluorine compound, nitric acid, azole, a water-soluble organic solvent, and water, and more preferably a peroxide. , Fluorine or fluorine compounds, nitric acid, azole, basic compounds, water-soluble organic solvents, and water, further preferably containing peroxides, fluorine or fluorine compounds, nitric acid, azoles, basic compounds, phosphoric acid, water-soluble organic solvents, and water.

In one aspect of the etching composition of the present invention, an etching composition containing peroxide, fluorine or a fluorine compound, nitric acid, azole, a basic compound, a urea-based hydrogen peroxide stabilizer, a water-soluble organic solvent, and water is preferred. Compounds, including etching compounds containing peroxide, nitric acid, azole, basic compounds, phosphoric acid, urea-based hydrogen peroxide stabilizers, water-soluble organic solvents, and water, or containing peroxides, fluorine or fluorine compounds, nitric acid, and azole , Alkaline compound, phosphoric acid, urea-based hydrogen peroxide stabilizer, water-soluble organic solvent and water etching composition. According to the etching composition of the present invention, the composition of the film can be changed according to the target film.

Regarding the etching composition of the present invention, when the pH is higher than 7, the peroxide is easily decomposed, and the pH is preferably less than 7. In the case where the layer containing titanium is etched, the titanium is easily dissolved. In other words, the pH is preferably 4 or less.

Second, the method for etching a single-layer film composed of copper, titanium, molybdenum, or nickel, a single-layer film containing an alloy of copper, titanium, molybdenum, or nickel, or a laminated film including the foregoing single-layer film, includes using The above-mentioned etching composition is subjected to an etching step. Furthermore, it includes the step of bringing the etching composition of the present invention into contact with an object to be etched. The etching target is as described above.

In addition, as a method for bringing the etching target into contact with the etching composition, a method of contacting the etching composition with the target by dripping (single-piece rotation processing) or spraying, or immersing the target in the etching composition can be generally used. Among these methods, a wet etching method such as a method is preferably a method in which an etching composition is dropped onto a target (single-piece rotation treatment) and brought into contact, and a method in which the target is dipped in the etching composition and brought into contact.

Regarding the use temperature of the etching composition, if the temperature of the etching composition is 20 ° C or higher, there is no case where the etching rate becomes too low and the production efficiency is significantly reduced. On the other hand, if the temperature is below the boiling point, it may be The composition is suppressed from changing and the etching conditions are kept constant. In this respect, the temperature of the etching treatment is preferably 15 ° C to 60 ° C, and particularly preferably 30 ° C to 50 ° C. By increasing the temperature of the etching composition, the etching rate is increased, but on the other hand, the optimum processing temperature can be appropriately determined on the basis of considering that the composition change of the etching composition is also kept small.

Furthermore, it may include manufacturing steps or packaging steps of a liquid crystal display, a color film, a touch panel, an organic EL display, an electronic paper, a MEMS, or an IC.

When etching is performed, the metal generated in the etching or the like is dissolved in the etching composition. If the etching composition is continuously used, the amount of metal dissolved in the etching composition or decomposition of the peroxide will cause changes in JET, S / E, and T / A. If these properties change, the cross-sectional shape will also change, so it is not possible to continue to make the same type of products. Therefore, in order to reduce costs and the like, a replenisher is usually used for the purpose of increasing the amount of dissolution of copper and other metals for long-term use. Consumption of organic acids. In this respect, in the present invention, one or two or more kinds of peroxides, nitric acid, fluorine and / or fluorine compounds, TMAH, or a water-soluble organic solvent used in the etching composition of the present invention may be replenished. A liquid is added to the etching composition used in the present invention. As a result, compared with the case where only an organic acid or a peroxide is used in a common etching composition, or both are added as a replenishing liquid, the life of the liquid is greatly extended.

Hereinafter, the present invention will be described in more detail with examples and comparative examples, but the present invention is not limited by these examples and the like.

1. Fabrication of metal substrate

‧Ti substrate production

Using glass as a substrate, titanium (Ti) was sputtered to form a barrier film made of titanium. Then, a resist is applied, the pattern mask is subjected to exposure and transfer, and then developed to produce a patterned titanium single-layer film. The film thickness of Ti is 1000 Å. The Ti substrate used in the following examples and comparative examples refers to this substrate.

‧Cu / Ti substrate production

Using glass as a substrate, titanium (Ti) was sputtered to form a barrier film made of titanium. Furthermore, copper wiring was sputtered to form copper wiring. Then, a resist is applied, the pattern mask is subjected to exposure transfer, and then developed to produce a patterned copper / titanium multilayer film. In addition, the film thickness of Cu / Ti is 5200Å / 250Å. The Cu / Ti substrate used in the following examples and comparative examples refers to this substrate.

‧CuNi / Cu / Ti substrate production

Using glass as a substrate, titanium (Ti) was sputtered to form a barrier film made of titanium. Then, copper wiring was sputtered to form a copper wiring, and copper nickel (CuNi) of a copper alloy was sputtered to form a protective film of copper. Then, a resist is applied, the pattern mask is subjected to exposure transfer, and then developed to produce a patterned copper alloy / copper / titanium multilayer film. In addition, the thickness of CuNi / Cu / Ti is 250Å / 5200Å / 250Å. The CuNi / Cu / Ti substrate used in the following examples and comparative examples refers to this substrate.

‧Cu / Mo substrate production

Using glass as a substrate, molybdenum (Mo) is sputtered to form a barrier made of molybdenum membrane. Then, copper wiring was formed by sputtering. Then, a resist is applied, the pattern mask is subjected to exposure transfer, and then developed to produce a patterned copper / molybdenum multilayer film. In addition, the film thickness of Cu / Mo is 5500Å / 300Å. The Cu / Mo substrate used in the following examples and comparative examples refers to this substrate.

2. Etching test

2-1. Etching test based on the addition of water-soluble organic solvents

An etching composition (Table 1) mixed with (A) hydrogen peroxide, (B) acidic ammonium fluoride, (C) nitric acid, (D) 5-amino-1H-tetrazole (ATZ), and water was added to In a beaker, the temperature was stabilized in a constant temperature bath maintained at 35 ° C. While the etching composition was stirred with a stirrer, a 1 cm × 1 cm Cu / Ti substrate was immersed, and the etching time was measured. The etching time measured at the time point at which copper and titanium disappeared was set as an appropriate amount of etching time, and about 1.5 times the amount of the appropriate amount of etching time was set as the actual etching time (that is, 50% of the excessive etching time, and this time was recorded 50% OE). An etching composition with 10% by weight, 20% by weight, and 30% by weight of dipropylene glycol (DPG) added to 100% by weight of the etching composition described in Table 1, and those described in Table 1 were prepared. An etching composition to which no DPG was added to the etching composition.

ATZ: 5-amino-1H-tetrazole

Next, each of the above-mentioned etching compositions was added to a beaker, and each of the Cu / Ti substrates was immersed while stirring with a stirrer, and an etching test was performed. Each of the substrates used in the test was set to Examples 1 to 3, respectively. In addition, Examples 1 to 3 refer to Cu / Ti substrates each containing 10% by weight, 20% by weight, and 30% by weight of DPG in the etching composition of Table 1 for the etching test. The etching time was performed by setting 1.5 times the appropriate amount of etching time described in Table 2 as the excessive etching time. Furthermore, after each of the Cu / Ti substrates subjected to the test was treated with water and dried, the cross-sectional shape was confirmed by SEM, and the side etching amount, taper angle, Ti residue, and smoothness of the resist pattern ends of each substrate were evaluated. Various properties such as cross-sectional shape. The above evaluation results are summarized in Table 2.

DPG: Dipropylene glycol

In each of the examples, all Ti residues were good, and the smoothness of the end portion of the resist pattern did not make the end portion uneven, and the cross-sectional shape was good. The SEM photograph of Example 1 is shown in FIG. 6.

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 above evaluation results are summarized in Table 3. In addition, Comparative Example 1 refers to a Ti substrate for which an etching test was performed without adding DPG to the etching composition of Table 1. Examples 4 to 6 refer to adding 10% by weight of each of the etching compositions in Table 1. 20% by weight and 30% by weight of DPG were used for the Ti substrate of the etching test. As a result, in the substrate of Comparative Example 1, the cross-sectional shape of Ti was hat-shaped as shown in FIG. 3, and T / A could not be measured. However, in the substrates of Examples 4 to 6, by adding DPG, the cross-sectional shape becomes good, and the smoothness of the end portions is improved. JET can also be controlled by the concentration of DPG added. The SEM photograph of Example 4 is shown in FIG. 9.

DPG: Dipropylene glycol

Regarding the Ti residue, A indicates good, and B indicates poor. Regarding the smoothness of the end of the resist pattern, A indicates good, and B indicates poor. The term "defective" means that the end portion is uneven. Regarding the cross-sectional shape, A indicates good, and B indicates poor (the same applies hereinafter).

2-2. Etching test based on the addition of water-soluble organic solvents

Use (A) Hydrogen peroxide, (B) Acid ammonium fluoride, (C) Nitric acid, (D) 5-Amino-1H-tetrazole (ATZ), (E) Tetramethylammonium hydroxide (TMAH ) And a water-containing etching composition (Table 4), an etching test was performed with a solution containing DPG and a solution without adding DPG. Using a Cu / Ti substrate, a Ti substrate, and a Cu / Mo substrate, the etching test was performed under the same test conditions as described above.

TMAH: Tetramethylammonium hydroxide

The results of the Cu / Ti substrate subjected to the etching treatment are summarized in Table 5. Comparative Example 2 refers to the Cu / Ti substrate used in the etching test without adding DPG to the etching composition of Table 4. Examples 7 to 9 refer to adding 10% by weight to the etching composition of Table 4, respectively. 20% by weight and 30% by weight of DPG were used for a Cu / Ti substrate for an etching test. The results show that by adding DPG in the laminated film, JET and T / A can also be controlled, and the ends of the resist pattern can be improved. Smoothness.

DPG: Dipropylene glycol

The results of the etching treatment of the Ti substrate are summarized in Table 6. In addition, Comparative Example 3 refers to a Ti substrate that was used in the etching test without adding DPG to the etching composition of Table 4, and Examples 10 to 12 refer to each of 10 weights added to the etching composition of Table 4. %, 20% by weight, and 30% by weight of DPG were used for the Ti substrate of the etching test. The results show that by adding DPG, JET can be controlled, and the smoothness or cross-sectional shape of the end of the resist pattern can be improved.

DPG: Dipropylene glycol

The results of the etching treatment of the Cu / Mo substrate are summarized in Table 7. In addition, Comparative Example 4 refers to the Cu / Mo substrate used for the etching test without adding DPG to the etching composition of Table 4, and Examples 13 and 14 refer to the addition of each of the etching compositions of Table 4 10% by weight and 20% by weight of DPG were used for a Cu / Mo substrate for an etching test. The results show that JET and T / A can also be controlled by adding DPG to the same single-layer film described above. In addition, the smoothness and cross-sectional shape of the end portion of each example were good.

DPG: Dipropylene glycol

2-3. Etching test based on the addition of water-soluble organic solvents

Using (A) hydrogen peroxide, (B) acid ammonium fluoride, (C) nitric acid, (D) 5-amino-1H-tetrazole (ATZ), (E) tetramethylammonium hydroxide (TMAH), (F) phosphoric acid and water etching composition (Table 8) A solution of DPG was added to perform an etching test. An etching test was performed using a CuNi / Cu / Ti substrate. The etching test was performed under the same test conditions as above except that O.E. was set to 50% or 100%.

The results of CuNi / Cu / Ti substrates treated with 50% O.E. are summarized in Table 9. In addition, Comparative Example 5 refers to the CuNi / Cu / Ti substrate used in the etching test without adding DPG to the etching composition of Table 8. Examples 15 to 17 refer to the etching composition of Table 8 respectively. A CuNi / Cu / Ti substrate was added to each of 10% by weight, 20% by weight, and 30% by weight of DPG for an etching test. The results show that by adding DPG, JET can be controlled. In each of the examples, all Ti residues were good, and with regard to the smoothness of the end portion of the resist pattern, the end portion did not become uneven, and the cross-sectional shape was good.

DPG: Dipropylene glycol

The results of CuNi / Cu / Ti substrates treated with 100% O.E. are summarized in Table 10. In addition, Comparative Example 6 refers to the CuNi / Cu / Ti substrate used in the etching test without adding DPG to the etching composition of Table 8. Examples 18 to 20 refer to the etching composition of Table 8 respectively. A CuNi / Cu / Ti substrate was added to each of 10% by weight, 20% by weight, and 30% by weight of DPG for an etching test. The results show that by adding DPG, JET can be controlled and the smoothness of the end of the resist pattern can be improved.

DPG: Dipropylene glycol

2-4. Etching test based on addition of water-soluble organic solvent

Use (A) Hydrogen peroxide, (B) Acid ammonium fluoride, (C) Nitric acid, (D) 5-Amino-1H-tetrazole (ATZ), (E) Tetramethylammonium hydroxide (TMAH ), (F) Phosphoric acid, (G) Phenylurea and water etching composition (Table 11) The solution added with DPG and the solution not added with DPG were subjected to an etching test. Using a CuNi / Cu / Ti substrate, a Cu / Ti substrate, and a Cu / Mo substrate, an etching test was performed. The O.E. was changed to 50% or 100%, and the etching test was performed under the same test conditions as described above.

The results of CuNi / Cu / Ti substrates treated with 50% O.E. are summarized in Table 12. In addition, Comparative Example 7 refers to a CuNi / Cu / Ti substrate for which an etching test was performed without adding DPG to the etching composition in Table 11, and Examples 21 to 23 refer to the etching composition in Table 11 respectively. A CuNi / Cu / Ti substrate was added to each of 10% by weight, 20% by weight, and 30% by weight of DPG for an etching test. The results show that by adding DPG, the JET, S / E, and T / A can be controlled, and the smoothness of the end of the resist pattern and the cross-sectional shape can also be improved. In addition, SEM photographs of Comparative Example 7 are shown in FIGS. 8 and 14, and SEM photographs of Example 23 are shown in FIG. 13.

DPG: Dipropylene glycol

In addition, Comparative Example 8 refers to the following CuNi / Cu / Ti substrate. When this CuNi / Cu / Ti substrate was made into the etching composition of Table 11, an etching composition without mixed phosphoric acid was separately prepared (that is, mixed with ( A) Hydrogen peroxide, (B) acidic ammonium fluoride, (C) nitric acid, (D) 5-amino-1H-tetrazole (ATZ), (E) tetramethylammonium hydroxide (TMAH), (G ) Etching composition of phenylurea and water), and no DPG was added to the etching composition for the etching test. The results of Comparative Example 7 and Comparative Example 8 show that if there is no phosphoric acid, the in-plane uniformity is greatly reduced, S / E is increased, and the smoothness or cross-sectional shape of the end portion is deteriorated. The reason for this is presumably that phenylurea was added. However, it has been shown that if a phosphoric acid-containing component is added to the component, that is, the etching composition of Table 11, and then DPG is added as a water-soluble organic solvent, the S / E or T / A can be easily controlled, and the resist can be greatly improved. The smoothness or cross-sectional shape of the pattern end. Based on the above, it is speculated that water-soluble organic solvents have the effect of further improving the efficacy of phosphoric acid.

The results of CuNi / Cu / Ti substrates treated with 100% O.E. are summarized in Table 13. In addition, Comparative Example 9 refers to the CuNi / Cu / Ti substrate used in the etching test without adding DPG to the etching composition of Table 11, and Examples 24 to 26 refer to the etching composition of Table 11 respectively. A CuNi / Cu / Ti substrate was added to each of 10% by weight, 20% by weight, and 30% by weight of DPG for an etching test. The results show that by adding DPG, JET, S / E, and T / A can be controlled, and the smoothness of the end of the resist pattern and the cross-sectional shape can also be improved.

DPG: Dipropylene glycol

The results of Cu / Ti substrates treated with 50% O.E. are summarized in Table 14. In addition, Comparative Example 10 refers to a Cu / Ti substrate used in the etching test without adding DPG to the etching composition of Table 11, and Examples 27 to 29 refer to adding each of the etching composition to Table 11 separately. 10% by weight, 20% by weight, and 30% by weight of DPG were used for a Cu / Ti substrate for an etching test. The results show that by adding DPG, JET, S / E, and T / A can be controlled. In each of the examples, all Ti residues were good, and the smoothness of the end portion of the resist pattern did not make the end portion uneven, and the cross-sectional shape was good.

DPG: Dipropylene glycol

In addition, Comparative Example 11 refers to the following Cu / Ti substrate. When the Cu / Ti substrate was prepared as the etching composition of Table 11, an etching composition not mixed with phosphoric acid (that is, mixed with (A) peroxidation) was separately produced. Hydrogen, (B) acid fluoride Ammonium, (C) nitric acid, (D) 5-amino-1H-tetrazole (ATZ), (E) tetramethylammonium hydroxide (TMAH), (G) phenylurea and water etching composition), No DPG was added to this etching composition, and it was used for an etching test. From the results of Comparative Example 10 and Comparative Example 11, since phosphoric acid was not contained, the end portion or cross-sectional shape of the resist pattern was deteriorated. The reason is speculated that phenylurea was added in the same manner as described above. However, it has been shown that if a phosphoric acid-containing component is added to this component, that is, DPG as a water-soluble organic solvent is added to the etching composition of Table 11, it is easy to control S / E or T / A, and the resist pattern can be greatly improved The smoothness or cross-sectional shape of the ends. From the above, it is estimated that the water-soluble organic solvent has the effect of further improving the efficacy of phosphoric acid, as described above.

The results of the Cu / Mo substrate treated with 50% O.E. are summarized in Table 15. In addition, Comparative Example 12 refers to the Cu / Mo substrate used for the etching test without adding DPG to the etching composition of Table 11, and Examples 30 to 32 refer to the addition of each of the etching compositions of Table 11 10% by weight, 20% by weight, and 30% by weight of DPG were used for a Cu / Mo substrate for an etching test. As a result, it was found that by adding DPG, JET and T / A can be controlled.

DPG: Dipropylene glycol

2-5. Etching test based on the addition of water-soluble organic solvents

(A) Hydrogen peroxide, (C) nitric acid, (D) 5-amino-1H-tetrazole (ATZ), (E) tetramethylammonium hydroxide (TMAH), (F) phosphoric acid, ( G) An etching test was performed on a solution containing phenylurea and water (Table 16) with a solution containing DPG and a solution without adding DPG. An etching test was performed using a Cu / Ti substrate. The O.E. was set to 50%, and the etching test was performed under the same test conditions as described above.

The results of the Cu / Ti substrate are summarized in Table 17. In addition, Comparative Example 13 refers to a Cu / Ti substrate used in the etching test without adding DPG to the etching composition of Table 16, and Example 33 refers to adding 30% by weight of DPG to the etching composition of Table 16. Cu / Ti substrate for etching test. The results show that by adding DPG, JET, S / E, T / A can be controlled, the disappearance of the resist pattern can be suppressed, the ends of the resist pattern can be smoothed, and the cross-sectional shape becomes positive. Cone. From this, it was confirmed that the Cu single-layer film also has the effect of adding a water-soluble organic solvent.

As described above, Mo or Ti is mainly used as a barrier metal for a Cu multilayer film. Depending on the purpose of the barrier metal, Ta or other metals, or an alloy made of several metals may be used. This situation shows that if the etching composition of the present invention is used, only the single-layer film of Cu can be selectively etched for the laminated film. This aspect suggests that, for the case where the barrier metal layer is to be treated with other etching compositions, etc., if the selective etching only dissolving Cu can be realized like the etching composition of the present invention, then other etching compositions are combined, By performing two-stage etching using two liquids, the laminated film can be processed into S / E or T / A within a predetermined range. In addition, it has been shown that when a substrate containing titanium is etched at one time, it can be performed with an etching composition containing fluorine or a fluorine compound. In contrast, when a substrate containing titanium is selectively etched, fluorine or fluorine is not used. The etching composition of the compound is performed.

DPG: Dipropylene glycol

2-6. Etching test based on additive

An etching composition (Table 18) using (A) hydrogen peroxide, (B) acid ammonium fluoride, (C) nitric acid, (D) 5-amino-1H-tetrazole (ATZ), and water, and An etching composition mixed with (A) hydrogen peroxide, (B) acid ammonium fluoride, (C) nitric acid, (D) 5-amino-1H-tetrazole (ATZ), (H) DPG, and water (Table) 19) The solution with additives added and the solution without additives were subjected to an etching test. An etching test was performed using a Cu / Ti substrate and a Cu / Mo substrate. The O.E. was set to 50%, and the etching test was performed under the same test conditions as described above. Furthermore, malonic acid used as an additive is added to improve the buffering effect of the solution and the solubility of Cu or Mo, and tetramethylammonium hydroxide (TMAH) is used to control the pH.

DPG: Dipropylene glycol

The results of the Cu / Ti substrate are summarized in Tables 20 and 21. It should be noted that Comparative Examples 14 to 18 refer to the etched composition in Table 18 in which malonic acid / TMAH was added at 0/2, 2/2, 2/3, 2/4, and 2/5% by weight, respectively. The Cu / Ti substrate was used for the etching test (Table 20). Examples 34 to 36 refer to Cu / Ti substrates in which the malic acid / TMAH was added to the etching composition of Table 19 at 0/0, 2/2, and 2/3% by weight, respectively, for the etching test ( Table 21). The results show that by adding DPG, the smoothness of the ends of the resist pattern can be improved. It is shown that if the pH is 5 or more, the solubility of Ti is greatly reduced, and therefore the pH of the Cu / Ti substrate is preferably 4 or less.

TMAH: Tetramethylammonium hydroxide

TMAH: Tetramethylammonium hydroxide

The results of the Cu / Mo substrate are summarized in Table 22 and Table 23. It should be noted that Comparative Examples 19 to 24 refer to the etching compositions in Table 18 in which C was added at 0%, 2/2, 2/3, 2/4, 2/5, and 2/6% by weight, respectively. Diacid / TMAH was used for the Cu / Mo substrate for the etching test (Table 22). Examples 37 to 39 refer to Cu / Mo substrates (see Table 19) in which the malonic acid / TMAH was added to each of the etching compositions of 2/2, 2/3, and 2/4% by weight for the etching test ( Table 23). The results show that the composition with DPG inhibits the undercut of Mo, so the pH range is wider than the composition without DPG. S / E, profile The shape improvement effect is also great. From Table 23, it was confirmed that undercutting of Mo does not occur when the pH is 4 or less. However, according to Table 22 and Table 23, if the composition of pH 4 is compared, the S / E of the substrate added with DPG and etched is very small compared to the substrate without DPG. Therefore, by adjusting the composition ratio, such as pH A composition of pH 5 or pH 6 can also suppress Mo undercutting. In addition, if the pH is 7 or more, there is a concern that the decomposition of hydrogen peroxide will be promoted. Therefore, it is presumed that the pH of the composition is effective to be less than 7. A SEM photograph of Comparative Example 21 is shown in FIG. 7, and a SEM photograph of Comparative Example 22 is shown in FIG. 13.

TMAH: Tetramethylammonium hydroxide

TMAH: Tetramethylammonium hydroxide

Next, Comparative Examples 25 to 30 shown below refer to the following Cu / Mo substrates. When the Cu / Mo substrates are made into the etching composition of Table 18, an etching composition without mixed acid ammonium fluoride is separately produced. (That is, an etching composition in which (A) hydrogen peroxide, (C) nitric acid, (D) 5-amino-1H-tetrazole (ATZ), and water is mixed) is mixed, and the etching composition is divided into 0/2, 2/2, 2/3, 2/4, 2 / 4.5, and 2 / 5.5% by weight of malonic acid / TMAH were added to the etching test (Table 24). As a result of Comparative Examples 25 to 30, relatively good cross-sectional shapes were obtained only at pH 2 to pH 3, but at other pHs, Cu or Mo did not dissolve, or Mo undercuts were generated. In addition, when compared with Comparative Examples 19 to 24, which were treated with an etching composition containing acidic ammonium fluoride, it was shown that acidic ammonium fluoride has the effect of suppressing the undercut of Mo, and further added as water solubility Organic solvent DPG, the effect of suppressing Mo undercut is further improved.

TMAH: Tetramethylammonium hydroxide

2-7. PH-Dependent Etching Test

An etching composition (Table 25) using (A) hydrogen peroxide, (B) acid ammonium fluoride, (C) nitric acid, (D) 5-amino-1H-tetrazole (ATZ), and water, and An etching composition mixed with (A) hydrogen peroxide, (B) acid ammonium fluoride, (C) nitric acid, (D) 5-amino-1H-tetrazole (ATZ), (H) DPG, and water (Table) 26) An etching test is performed. An etching test was performed using a Cu / Ti substrate. The O.E. was set to 50%, and the etching test was performed under the same test conditions as described above. Furthermore, the citric acid used in the additive is added to improve the buffering effect of the solution and the solubility of Cu or Ti, and TMAH is used to control the pH.

The results of the Cu / Ti substrate are summarized in Tables 27 and 28. In addition, Comparative Examples 31 to 33 are Cu / Ti added to the etching composition of Table 25 at 10/2, 10/3, and 10/8% by weight of citric acid / TMAH for each etching test. Substrate (Table 27), Example 40 to Example 42 refer to the etching composition in Table 26 by adding citric acid / TMAH at 10/2, 10/3, and 10/8% by weight, respectively, for the etching test. Cu / Ti substrate (Table 28). As a result, S / E becomes larger as the pH increases. However, it was shown that a substrate with DPG added suppressed S / E rise compared to a substrate without DPG added. In addition, although the end portion of the resist pattern showing the substrate to which DPG is not added is uneven, the substrate to which DPG is added can smooth the end portion.

TMAH: Tetramethylammonium hydroxide

TMAH: Tetramethylammonium hydroxide

The results of the Cu / Mo substrate are summarized in Tables 29 and 30. In addition, Comparative Example 36 to Comparative Example 39 refer to the etching composition of Table 25 in which the citric acid / TMAH was added at 10%, 10/3, 10/8, and 10/10 wt%, respectively, for the etching test. For Cu / Ti substrates (Table 29), Examples 43 to 46 refer to the etched composition in Table 26 at 10/2, 10/3, 10/8, and 10/10 wt% of citric acid, respectively. / TMAH and a Cu / Mo substrate for an etching test (Table 30). As a result, the substrates treated with the composition of Table 25 all undercut Mo. However, when S / E is compared, it is shown that the substrate with no DPG increases in S / E as the pH rises. In contrast, the substrate with DPG suppresses S / E. In addition, it is shown that the end of the resist pattern on the substrate without DPG becomes uneven, but the substrate with DPG added can be smooth. All the substrates in Table 29 produced Mo undercuts. However, it is suggested that by adjusting the composition ratio in the same manner as in the case of using malonic acid, it can be suppressed. Mo undercut. Furthermore, it has been suggested that S / E can be suppressed by adding DPG. Furthermore, if the pH is 7 or more in the same manner as when malonic acid is used instead of citric acid, the decomposition of peroxides may be promoted. Therefore, it is estimated that the pH range is effective to be less than 7.

TMAH: Tetramethylammonium hydroxide

TMAH: Tetramethylammonium hydroxide

2-8. Etching test based on the addition of water-soluble organic solvents

Use (A) Hydrogen peroxide, (B) Acid ammonium fluoride, (C) Nitric acid, (D) 5-Amino-1H-tetrazole (ATZ), (E) Tetramethylammonium hydroxide (TMAH ), (G) phenylurea and water etching composition (Table 31) were added 2-propanol (IPA), diethylene glycol (DEG), dimethylsulfinium (DMSO), 1,3- Butanediol (BD), 1,3-dimethyl-2-imidazolidinone (DMI), N-methyl-2-pyrrolidone (NMP), glycerol (Gly), N, N-dimethyl The acetamide (DMAc) solution and the unadded solution were subjected to an etching test. An etching test was performed using a CuNi / Cu / Ti substrate. The O.E. was set to 50%, and the etching test was performed under the same test conditions as described above.

The results obtained by etching the CuNi / Cu / Ti substrate using IPA as the water-soluble organic solvent are summarized in Table 32. It should be noted that Comparative Example 40 refers to an etching test without adding IPA to the etching composition shown in Table 31. Examples 47 to 49 of CuNi / Cu / Ti substrates refer to CuNi / Cu for the etching test by adding 10%, 20%, and 30% by weight of IPA to the etching composition in Table 31, respectively. / Ti substrate. The results show that, compared with the substrate without addition, the IPA can also control JET, S / E, and T / A, smooth the end of the resist pattern, and make the cross-sectional shape a forward cone.

IPA: 2-propanol

The results obtained by etching the CuNi / Cu / Ti substrate using DEG and DMSO as water-soluble organic solvents are summarized in Table 33. In addition, Examples 50 to 52 refer to CuNi / Cu / Ti substrates for which an etching composition of Table 31 was added with 10% by weight, 20% by weight, and 30% by weight of DEG for the etching test. Examples 53 to 55 refer to 10% by weight, 20% of each added to the etching composition of Table 31. A CuNi / Cu / Ti substrate for an etching test was prepared by using DMSO of 30% by weight and 30% by weight. The results show that, compared with the substrate without DEG or DEG or DMSO, JET, S / E, and T / A can also be controlled to smooth the ends of the resist pattern and make the cross-sectional shape a forward cone.

DEG: Diethylene glycol, DMSO: Dimethyl sulfene

The results obtained by etching the CuNi / Cu / Ti substrate using BD and DMI as water-soluble organic solvents are summarized in Table 34. In addition, Examples 56 to 58 refer to CuNi / Cu / Ti substrates for which an etching composition of Table 31 was added with 10% by weight, 20% by weight, and 30% by weight of BD, respectively, for the etching test. Examples 59 to 61 refer to adding 10% by weight, 20% by weight, and 30% to the etching composition in Table 31, respectively. A CuNi / Cu / Ti substrate was used for the etching test with DMI by weight. The results show that, compared with the BD or DMI, compared with the unadded substrate, JET, S / E, and T / A can also be controlled, the ends of the resist pattern can be smoothed, and the cross-sectional shape can be made a forward cone.

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

The results obtained by etching the CuNi / Cu / Ti substrate using NMP and Gly as water-soluble organic solvents are summarized in Table 35. In addition, Examples 62 to 64 refer to CuNi / Cu / Ti substrates for which an etching composition of Table 31 was added with 10% by weight, 20% by weight, and 30% by weight of NMP, respectively, for the etching test. Examples 65 to 67 refer to CuNi / Cu / Ti substrates each containing 10% by weight, 20% by weight, and 30% by weight of Gly added to the etching composition of Table 31 for the etching test. Results show It shows that NMP or Gly can also control JET, S / E, T / A, and make the end of the resist pattern smoother than the non-added substrate.

NMP: N-methyl-2-pyrrolidone, Gly: glycerol

The results obtained by etching the CuNi / Cu / Ti substrate using DMAc as a water-soluble organic solvent are summarized in Table 36. In addition, Examples 68 to 70 refer to CuNi / Cu / Ti substrates each containing 10% by weight, 20% by weight, and 30% by weight of DMAc added to the etching composition of Table 31 for the etching test. As a result, it can be known that, compared with the substrate not added, DMAc can also control JET, S / E, and T / A, smooth the end of the resist pattern, and make the cross-sectional shape a forward cone.

[TABLE 36]

DMAc: N, N-dimethylacetamide

According to the above results, by using a water-soluble organic solvent, it is possible to control JET, S / E, and T / A, thereby smoothing the ends of the resist pattern and making the cross-sectional shape a forward cone.

2-9. Peroxide-based etching test

Using (A) ammonium peroxodisulfate, (B) acid ammonium fluoride, (C) nitric acid, (D) 5-amino-1H-tetrazole (ATZ), (G) phenylurea and water The etching composition (Table 37) was subjected to an etching test. An etching test was performed using a CuNi / Cu / Ti substrate. The O.E. was set to 50%, and the etching test was performed under the same test conditions as described above.

The results of the CuNi / Cu / Ti substrate are summarized in Table 38. In addition, Comparative Example 41 refers to the CuNi / Cu / Ti substrate used in the etching test without adding DPG to the etching composition of Table 37, and Examples 71 and 72 refer to the etching composition of Table 37, respectively. A CuNi / Cu / Ti substrate was added to each of 10% by weight and 20% by weight of DPG for an etching test. The results show that the substrate with DPG can control JET, S / E, and T / A compared with the substrate without DPG, and the cross-sectional shape can be made into a forward tapered shape. In this way, peroxides such as ammonium peroxodisulfate can also obtain substantially the same effects as hydrogen peroxide, so ammonium peroxodisulfate can replace hydrogen peroxide.

DPG: Dipropylene glycol

3. Fluid life and supply test

3-1. Liquid life evaluation test

Use (A) Hydrogen peroxide, (B) Hydrofluoric acid, (C) Nitric acid, (D) 5- Etching composition of amino-1H-tetrazole (ATZ), (E) TMAH, (G) phenylurea, (H) DPG and water (Table 39) was subjected to a liquid life evaluation test. The liquid life evaluation test is a test to confirm the change in performance when the amount of copper dissolved increases. In addition, regarding the dissolution of copper, a test was performed in which a copper powder was dissolved instead of a copper substrate. The substrate used for the test was an etching test using a CuNi / Cu / Ti substrate. The O.E. was set to 50%, and the etching test was performed under the same test conditions as described above.

DPG: Dipropylene glycol

The results of the CuNi / Cu / Ti substrate are summarized in Table 40. In addition, Example 74 refers to the CuNi / Cu / Ti substrate treated with the etching composition without adding copper to the etching composition in Table 39, and Examples 75 to 77 refer to the etching composition in Table 39. A CuNi / Cu / Ti substrate treated with an etching composition having a copper content of 1,000 ppm, 2000 ppm, and 3000 ppm, respectively, treated therein. In Comparative Examples 75 to 77, which were treated with an etching composition in which 0 ppm to 2000 ppm of copper was dissolved, the performance slowly decreased. In addition, it shows the implementation of processing with an etching composition in which 3000 ppm of copper is dissolved. In Example 77, the performance was greatly reduced, and Ti residue was generated. Although not shown in the following table, if copper is added in an amount of up to 4000 ppm, copper itself is not completely dissolved in the etching composition.

3-2. Liquid life supply test

Next, add an etching composition (Table 41) in which the etching composition of Table 39 is mixed with (A) hydrogen peroxide, (B) hydrofluoric acid, (C) nitric acid, (D) TMAH, and water as a replenishing solution. The composition is subjected to a liquid life replenishment test. In addition, the method for adding a replenishment liquid is used in the form of an etching composition in which a replenishment liquid having a volume of 1.8 vol% or 2.0 vol% relative to the volume of the etching composition is added per 1,000 ppm of copper dissolved. The substrate used for the test was an etching test using a CuNi / Cu / Ti substrate. The O.E. was set to 50%, and the etching test was performed under the same test conditions as described above.

[TABLE 41]

The results of the CuNi / Cu / Ti substrate are summarized in Table 42. In addition, Example 78 refers to a CuNi / Cu / Ti substrate treated with an etching composition in which the additional copper powder and supplement liquid are not added to the etching composition of Table 39. Examples 79 to 82 are shown in Table The etching composition of 39 was added with 8,000 ppm, 16000 ppm, 24000 ppm, and 32,000 ppm of copper powder, and further added 14.4 vol%, 32.0 vol%, 46.8 vol%, and 62.4 vol% of the etching composition of Table 41. CuNi / Cu / Ti substrate. The results show that in Example 77, Ti residue was generated when the copper dissolved amount was 3000 ppm. In contrast, in Example 82, even if copper was dissolved at 32,000 ppm, Ti residue was not generated. In addition, it was also shown that the performance was maintained approximately the same as the initial performance. From this, it was confirmed that by adding a composition containing peroxide, nitric acid, fluorine and / or fluorine compounds, TMAH, or a water-soluble organic solvent to the etching composition used in the present invention as a replenishing liquid, the liquid can be extended. life.

[Table 42] CuNi / Cu / Ti substrate (CuNi / Cu / Ti = 250Å / 5200Å / 250Å), 50% OE

(Industrial availability)

If the etching composition of the present invention is used for etching, a single-layer film and / or a laminated film can be etched at one time, a complex and delicate 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 higher-performance flat panel display and the like. Furthermore, by using a replenisher liquid, the life of the liquid can be prolonged, thereby contributing to reducing the production cost of the substrate and improving safety.

Claims (20)

An etching composition for etching the following single-layer film or laminated film, the single-layer film is composed of a metal selected from the group consisting of copper, titanium, molybdenum, and nickel, or a nitride of these metals, or It is composed of one or two or more alloys selected from the group consisting of copper, titanium, molybdenum, and nickel. The laminated film includes one or more layers of the single-layer film and the etching composition. Materials include azole, nitric acid, peroxide, and water-soluble organic solvents. The etching composition according to claim 1, wherein a vapor pressure of the water-soluble organic solvent at 25 ° C is 2 kPa or less. The etching composition according to claim 1 or 2, wherein the water-soluble organic solvent is selected from the group consisting of alcohol, glycol, glycol, triol, ketone, carbonate, and sulfonium. 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 persulfate, sodium persulfate, and potassium persulfate. The etching composition according to any one of claims 1 to 5, further comprising 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 a quaternary ammonium hydroxide and ammonia water. The etching composition according to any one of claims 1 to 7, 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, acid ammonium fluoride, and hydrofluoric acid. The etching composition according to any one of claims 1 to 9, further comprising a urea compound. 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 any one of claims 1 to 11, further comprising an organic acid. The etching composition according to claim 12, wherein the organic acid is malonic acid or citric acid. The etching composition according to any one of claims 1 to 13, which contains 1 to 15% by mass of peroxide, 1 to 10% by mass of nitric acid, and 0.005 to 0.2% by mass of azole. Type, 0.05 mass% to 1.00 mass% of a fluorine compound, and 1 mass% to 50 mass% of a water-soluble organic solvent. The etching composition according to any one of claims 1 to 14 is used to etch a laminated film, and the laminated film is composed of a titanium / copper / titanium layer. The etching composition according to any one of claims 1 to 14 is used to etch a laminated film, and the laminated film is composed of an alloy / copper / titanium layer made of copper and nickel, and the titanium is located on the substrate side. The etching composition according to any one of claims 1 to 14, which is used to etch a laminated film, and the laminated films are each a single layer of copper / a single layer of molybdenum, and the aforementioned single layer of molybdenum is located on the substrate side. The etching composition according to any one of claims 1 to 17, whose pH does not reach 7.0. A method for etching the following single-layer film or multilayer film, the single-layer film is composed of a metal selected from the group consisting of copper, titanium, molybdenum, and nickel, or a nitride of these metals, or is composed of Free copper, titanium, molybdenum and nickel are composed of one or two or more alloys. The aforementioned laminated film includes one or two or more of the aforementioned single-layer films, and the aforementioned method includes the use of the item as requested The etching step of the etching composition according to any one of 1 to 18. The method according to claim 19 is used for manufacturing steps or packaging steps of a liquid crystal display, a color film, a touch panel, an organic electroluminescence display, an electronic paper, a micro-electro-mechanical system, or an integrated circuit.