TWI624565B - Etching solution for multilayer film, etching concentrate, and etching method - Google Patents

Abstract

In the etching liquid of the multilayer film in which the copper layer and the molybdenum layer are etched by one liquid, the cross-sectional shape of the edge after etching is required to be a so-called shape without a downward taper, and no precipitate is generated in the etching liquid. When used in mass production.

An etching solution for a multilayer film comprising hydrogen peroxide, an inorganic acid, an acidic organic acid, a neutral organic acid, an amine compound, and a hydrogen peroxide decomposition inhibitor, and comprising a copper layer and a molybdenum layer, does not contain an azole compound, and therefore No reactant was formed between the hydrogen peroxide, and no precipitate was produced in the etching solution. Moreover, the cross-sectional shape of the edge after etching can be a shape that is ideally tapered. Further, since the phosphorus compound and the fluorine compound are not contained, the environmental load is also reduced when discarded.

Description

Etching solution for multilayer film, etching concentrate, and etching method

The present invention relates to an etching solution for a multilayer film, an etching concentrate, and an etching method, which are used when etching a multilayer film of a copper layer and a molybdenum layer used for wiring a flat panel display such as a liquid crystal or an organic EL.

A TFT (Thin Film Transistor) of a flat panel display (FPD) such as a liquid crystal or an organic EL (Electro-Luminescence) is made of aluminum as a wiring material. In recent years, large-screen and high-definition FPD systems have been popularized, and wiring materials used have required lower resistance than aluminum. Therefore, in recent years, copper having a low electrical resistance lower than that of aluminum has been used as a wiring material.

When copper is used as the wiring material, there are two problems of bonding force between the substrate and diffusion of the semiconductor substrate. In other words, in the state in which the gate wiring is used, even if a sputtering method in which the impact energy to the substrate is relatively large is used, there is a state in which the bonding force is not sufficient between the substrates of the glass or the like. . In addition, it is used in the source ^. In the state of the drain wiring, there is a problem that the so-called adhered copper is diffused to become the base and the electrical design value of the semiconductor is changed.

In order to solve this problem, therefore, it is now employed to form a molybdenum layer on a substrate or a semiconductor substrate, on which a multilayer of copper layers is formed. Made.

The FPD wiring is a multilayer film formed by sputtering by wet etching to form an FPD wiring. Since a large area can be formed in one breath, the process can be shortened. Here, the wet etching of the wiring is important in the following aspects.

(1) The machining accuracy is improved in the same manner.

(2) The wiring profile after processing is a straight angle of the specified angle.

(3) Since copper ions are contained in the etching liquid, the etching performance is not easily deteriorated (the plating bath life becomes long).

(4) The production of precipitates is reduced.

In the same manner as the first item, the improvement of the machining accuracy is not only wet etching, but also a required item in the state where the processing of the micro area is performed. The shape of the wiring section to be the second item is a shape necessary for forming a large-area FPD wiring in order to form a reliable wiring. This is because if the edge portion of the etching of the multilayer film of the copper layer and the molybdenum layer is formed by a smooth taper of 30 to 60 degrees from the substrate, it is assumed that etching failure occurs, even if the etching speed of copper and molybdenum is balanced. Differently, it is also possible to ensure that the quality of the product can be ensured.

The third item is the life of the etchant itself. In order to etch a large-area substrate, a large amount of etching liquid is required. These etching liquids are also used cyclically from the viewpoint of cost. The period (life) at which the etching performance can be maintained is as long as possible, and the cost becomes relatively inexpensive.

In addition, the fourth project is not only a problem for maintaining the etching device, but also a problem with the quality of the product. Due to etching When a precipitate is generated, the piping of the etching apparatus is clogged, or the hole of the shower nozzle for spreading the etching liquid is blocked. These phenomena are responsible for stopping the operation of the etching device and are related to an increase in cost. Further, when the precipitate adheres to the product through the etching liquid, it is a cause of short-circuiting or disconnection, and is directly related to the quality of the product.

In the etchant of the multilayer film of the copper layer and the molybdenum layer, it is reported that the etching liquid containing at least one hydrogen peroxide selected from the neutral salt and the organic acid (Patent Document 1: JP-A-2002-302780) Bulletin (Japanese Patent No. 4282927)).

Further, it is reported that a predetermined amount of hydrogen peroxide, an organic acid, a phosphate, a water-soluble cyclic amine compound as a first additive, a water-soluble compound containing one of an amine group and a carboxyl group as a second additive, and a fluorine compound are respectively contained. And an etching solution of a copper-molybdenum film which is deionized from water (Patent Document 2: JP-A-2004-193620 (Japanese Patent No. 4,438,322)).

In addition, it is reported that an etching liquid for a multilayer film wiring containing hydrogen peroxide, an organic acid, a triazole compound, a fluorine compound, and molybdenum/copper/molybdenum nitride of ultrapure water (Patent Document 3: JP-A-2007-005790) Bulletin (Japanese Patent No. 5111790)).

Further, an etching solution for a multilayer film is disclosed which comprises (A) hydrogen peroxide, (B) an inorganic acid containing no fluorine atom, (C) succinic acid, glycolic acid, lactic acid, malonic acid, and malic acid. And at least one selected organic acid, (D) an amine compound having a carbon number of 2 to 10 and having an amine group and a hydroxyl group and having a total of two or more, (E) 5-amino-1H-tetrazole, and F) Hydrogen peroxide stabilizer containing a copper layer and a molybdenum layer having a pH of 2.5 to 5 (Patent Document 4: Japanese) Patent No. 5,051,323).

[Previous Technical Literature]

[Patent Literature]

[Patent Document 1] Japanese Laid-Open Patent Publication No. 2002-302780 (Japanese Patent No. 4282927)

[Patent Document 2] Japanese Laid-Open Patent Publication No. 2004-193620 (Japanese Patent No. 4,438,322)

[Patent Document 3] Japanese Laid-Open Patent Publication No. 2007-005790 (Japanese Patent No. 5111790)

[Patent Document 4] Japanese Patent No. 5051223

Patent Document 1 discloses only that in the state of a mixed liquid of hydrogen peroxide and an organic acid, if the ratio of hydrogen peroxide is adjusted, the contents of copper and molybdenum can be simultaneously etched, but regarding the composition of the specific etching liquid , there is no disclosure at all.

Patent Documents 2 and 3 use a fluorine compound in the composition. Therefore, there is a problem that not only the glass substrate or the tantalum substrate is etched, but also the environmental load is increased when the etching liquid is discarded.

Patent Document 4 examines etching of a multilayer film of a copper layer and a molybdenum layer to a thin portion. However, the composition of the etching liquid of Patent Document 4 has a problem that a large amount of precipitates are generated in the etching liquid.

In addition, a phosphorus compound or a fluorine compound is used as an etching liquid. In the case of the composition, it is easy to require performance as an etching liquid, but on the other hand, when it is discarded, the load on the environment is increased.

The present invention has been conceived in view of the above problems, and provides an etching liquid composition comprising a multilayer film of a copper layer and a molybdenum layer, which satisfies the importance of wet etching of wiring described in [Background Art]. In particular, an etching liquid, a concentrated liquid, and an etching method for which no precipitate is generated in the etching liquid and the load on the environment is not increased when discarded is provided.

More specifically, the etching solution for a multilayer film comprising a copper layer and a molybdenum layer according to the present invention is characterized by comprising hydrogen peroxide, an inorganic acid, an acidic organic acid, a neutral organic acid, an amine compound, and decomposition inhibition of hydrogen peroxide. Agent.

Further, since the etching liquid of the present invention does not increase in volume at the time of storage or transfer, it can be constituted by the state of the concentrated liquid. More specifically, the present invention provides an etching concentrate for a multilayer film comprising a copper layer and a molybdenum layer, comprising: an inorganic acid, an acidic organic acid, a neutral organic acid, an amine compound, a hydrogen peroxide decomposition inhibitor, and water. .

Further, the etching method for a multilayer film comprising a copper layer and a molybdenum layer according to the present invention comprises: etching comprising a mineral acid, an acidic organic acid, a neutral organic acid, an amine compound, a hydrogen peroxide decomposition inhibitor, and water. The process of adjusting the etching liquid for the multilayer film by blending the concentrated liquid, water and hydrogen peroxide, and the process of contacting the above-mentioned multilayer film with the etching liquid to the substrate to be processed.

The cross-sectional shape of the wiring for etching liquid etching of the present invention is a straight cone Shape, and maintain its shape even if it is over-etched. In addition, since it is a structure which does not contain an azole compound which forms a precipitate when hydrogen peroxide is used together, in the etching liquid, no precipitate is generated, and there is no accident such as clogging of the pipe or clogging of the nozzle of the shower nozzle. Therefore, it is not necessary to stop the operation of the etching apparatus due to the occurrence of precipitates, and stable production can be performed.

Further, since the etching concentrate of the present invention does not contain hydrogen peroxide derived from the etching liquid described above and a predetermined amount of water, the volume can be increased without increasing the volume, and the storage or transfer can be carried out almost without causing changes over time. Further, since the concentrate and the hydrogen peroxide are separately etched and taken and treated, the concentration adjustment of the etching liquid which changes the concentration of the component with use can be easily performed.

In addition, the etching method of the present invention blends the etching concentrate and the hydrogen peroxide water to blend the etching liquid and contact the substrate to be processed. Therefore, the etching liquid of the stable composition can be prepared at any time, and the profile of the wiring formed is smooth. The taper, even if over-etched, allows the taper angle to be maintained at an appropriate angular extent.

Further, since the etching liquid of the present invention does not contain a substance including a phosphorus compound, a chlorine compound, and a fluorine compound, there is an advantage that the load on the environment is light when discarded.

1‧‧‧Substrate

2‧‧‧ copper layer

3‧‧‧ molybdenum layer

4‧‧‧Resist (layer)

5‧‧‧ cone angle

6‧‧‧Sloping surface

10‧‧‧Under the cut

Fig. 1 is a conceptual view showing a cross section of a wiring formed by etching.

Hereinafter, the etching liquid of the present invention will be described. In addition, the following description shows an embodiment of the etching solution of the present invention, which may be The following embodiments and examples are modified within the scope of the gist of the invention. The etching liquid of the present invention is characterized in that it does not generate precipitates in the etching liquid. Even as shown in the examples described later, the reactants of the azole compound and hydrogen peroxide are strongly indicated. Thus, the etching solution of the present invention does not contain an azole compound.

Further, in order to reduce the environmental load, the phosphorus compound, the fluorine compound, and the chlorine compound are not contained. However, the phosphorus compound, the fluorine compound, and the chlorine compound may be contained in a state in which the environmental performance of the etching performance and the quality of the product is not affected or the environmental load at the time of disposal is below the standard established by each country. In addition, if it is such a quantity, it can be interpreted as being non-contained.

<hydrogen peroxide>

Copper etching is oxidized by copper to form copper oxide (CuO), which is dissolved by a mineral acid. Further, the etching of molybdenum is oxidized to become molybdenum oxide (MoO ₃ ), which is dissolved by water. Hydrogen peroxide is used as an oxidizing agent for copper oxide and molybdenum. The hydrogen peroxide is preferably 3.50% by mass to 5.80% by mass based on the total amount of the etching solution. In addition, hydrogen peroxide is also called "hydrogen peroxide water".

<Inorganic acid>

The inorganic acid is used to dissolve the oxidized copper. In order to reduce the environmental load on the substrate material of the so-called glass or tantalum, and in order to reduce the environmental load when the etching liquid is discarded, the phosphorus compound and the fluorine compound are not used. In addition, no hydrochloric acid was used. Nitric acid and sulfuric acid can be used moderately. The inorganic acid is contained in an inorganic acid in an amount of from 0.01% by mass to 0.50% by mass, preferably from 0.02% by mass to 0.20% by mass, based on the total amount of the etching solution.

<organic acid>

The organic acid component mainly functions to adjust the taper angle of the cross section of the etched wiring. In addition, it is considered to have a certain degree of inhibition of the decomposition of hydrogen peroxide. In the organic acid component, a combination of an acidic organic acid and a neutral organic acid is used. Further, it is also possible to combine both an acidic organic acid and a neutral organic acid.

The organic acid to be used is preferably an aliphatic carboxylic acid having 1 to 18 carbon atoms or an aromatic carboxylic acid having 6 to 10 carbon atoms, and preferably an amino acid having 1 to 10 carbon atoms.

The aliphatic carboxylic acid having 1 to 18 carbon atoms is preferably classified into formic acid, acetic acid, propionic acid, lactic acid, glycolic acid, diglycolic acid, pyruvic acid, malonic acid, butyric acid, hydroxybutyric acid, Tartaric acid, succinic acid, malic acid, maleic acid, fumaric acid, oxalic acid, glutaric acid, itaconic acid, adipic acid, caproic acid, adipic acid, citric acid, propane tricarboxylic acid, trans- Aconitine, heptanoic acid, octanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, and the like.

The aromatic carboxylic acid having 6 to 10 carbon atoms is preferably benzoic acid, salicylic acid, mandelic acid, phthalic acid, isophthalic acid or terephthalic acid.

Further, as the amino acid having 1 to 10 carbon atoms, an amino acid, an alanine, a glycine, an aspartic acid, an aspartic acid, a creatinine, a serine, a glutamine, or a glutamine are preferable. Acid, 4-aminobutyric acid, iminodibutyric acid, arginine, leucine, isoleucine, cyanotriacetic acid, and the like.

Among the above-mentioned organic acids, glycolic acid, aspartic acid, glutamic acid, and citric acid can be suitably used as the acidic organic acid system. In particular, glycolic acid, aspartic acid, and glutamic acid can be obtained by using three kinds at the same time. Appropriate characteristics. Further, the acidic organic acid is preferably contained in an amount of from 1% by mass to 7% by mass based on the total amount of the etching solution.

Further, in the state in which glycolic acid, aspartic acid, and glutamic acid are simultaneously used, the glycolic acid acid may preferably be contained in an amount of 1% by mass to 5% by mass based on the total amount of the etching liquid, more preferably 1.50% by mass to 2.50% by mass. Further, the aspartic acid may preferably be contained in an amount of from 0.10% by mass to 1.00% by mass, more preferably from 0.20% by mass to 0.50% by mass, based on the total amount of the etching solution. Further, the glutamic acid system may preferably be contained in an amount of 0.1% by mass to 1.0% by mass, more preferably 0.60% by mass to 0.90% by mass based on the total amount of the etching liquid.

Further, as the neutral organic acid system, glycine acid, alanine or beta alanine can be suitably used. Further, the neutral organic acid is preferably contained in an amount of from 0.10% by mass to 3.00% by mass based on the total amount of the etching solution.

Further, in addition to the above, one type of glycolic acid and one of other acidic organic acids or one of neutral organic acids may be combined. In this state, the glycolic acid is preferably contained in an amount of from 1% by mass to 5% by mass, more preferably from 1.50% by mass to 2.30% by mass, based on the total amount of the etching solution. On the other hand, the acidic organic acid or the neutral organic acid may preferably be contained in an amount of 0.10% by mass to 1.00% by mass, more preferably 0.3% by mass to 0.7% by mass based on the total amount of the etching liquid.

<amine compound>

The amine compound is mainly responsible for the adjustment of the pH of the etching solution. As the amine compound, those having a carbon number of 2 to 10 can be suitably used.

More preferably, it is more specifically listed as ethyl diamine, trimethylene diamine, tetramethylene diamine, 1,2-propane diamine, 1,3-propane diamine, N, N-di Methyl-1,3-propanediamine, N,N-diethyl-1,3-propanediamine, 1,3-diaminobutane, 2,3-diaminobutane, penta Diamine, 2,4-diaminopentane, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, ninethylenediamine, N-methylexylethyl Amine, N,N-dimethylethylidene diamine, trimethylethylidene diamine, N-ethylethylidene diamine, N,N-diethylethylenediamine, triethylethyl Diamine, 1,2,3-triaminopropane, hydrazine, tris(2-aminoethyl)amine, tetrakis(aminomethyl)methane, di-ethyltriamine, tri-ethylidene Polyamines such as tetraethylpentamine, heptaethylamine, octadecylethylamine, dinonylcycloundecene, etc.; ethanolamine, N-methylethanolamine, N-methyldiethanolamine, N -ethylethanolamine, N-aminoethylethanolamine, N-propylethanolamine, N-butylethanolamine, diethanolamine, triethanolamine, 1-amino-2-propanol, N-methylisopropanolamine, N-ethylisopropanolamine, N-propyl isopropanolamine, 2-aminopropan-1-ol, N-methyl-2-amino-propan-1-ol, N-ethyl-2 -Amino-propan-1-ol, 1-aminopropane-3-ol, N-A Base-1-aminopropan-3-ol, N-ethyl-1-aminopropan-3-ol, 1-aminobutan-2-ol, N-methyl-1-aminobutane- 2-alcohol, N-ethyl-1-aminobutan-2-ol, 2-aminobutan-1-ol, N-methyl-2-aminobutan-1-ol, N-B Benzylaminobutan-1-ol, 3-aminobutan-1-ol, N-methyl-3-aminobutan-1-ol, N-ethyl-3-aminobutyl Alkan-1-ol, 1-aminobutan-4-ol, N-methyl 1-aminobutan-4-ol, N-ethyl-1-aminobutan-4-ol, 1- Amino-2-methylpropan-2-ol, 2-amino-2-methylpropan-1-ol, 1-aminopentan-4-ol, 2-amino-4-methylpentane -1-ol, 2-aminohexane-1-ol, 3-aminoheptane-4-ol, 1-aminooctane-2 - alcohol, 5-aminooctane-4-ol, 1-aminopropane-2,3-diol, 2-aminopropane-1,3-diol, tris(hydroxyethyl)aminomethane, 1,2-diaminopropan-3-ol, 1,3-diaminopropan-2-ol, 2-(2-aminoethoxy)ethanol, 2-(2-aminoethylamino group An alkanolamine such as ethanol or diethylene glycol amine, and these may be used singly or in combination of plural kinds. Even among these, 1-amino-2-propanol is particularly preferred. Further, the amine compound may preferably be contained in an amount of from 0.50% by mass to 2.00% by mass, more preferably from 1.00% by mass to 1.90% by mass, based on the total amount of the etching solution.

<Hydrogen peroxide decomposition inhibitor>

In the etching liquid of the present invention, hydrogen peroxide is used as the oxidizing agent. The hydrogen peroxide is decomposed by itself, and therefore, a decomposition inhibitor for suppressing decomposition thereof is added. In order to increase the life of the etching solution. The main hydrogen peroxide decomposition inhibitor is preferably a phenyl group other than a urea-based hydrogen peroxide stabilizer such as phenyl urea, allyl urea, 1,3-dimethyl urea or thiourea. Ammonium acetate, phenylethylethylene glycol or a lower alcohol such as 1-propanol or 2-propanol.

Even in the case, it is particularly preferable to use phenyl urea, and it is more desirable to use phenyl urea and 1-propanol in combination. When the hydrogen peroxide decomposition inhibitor is phenyl urea, it is preferably contained in an amount of 0.05% by mass to 0.20% by mass, more preferably 0.07% by mass to 0.12% by mass based on the total amount of the etching solution. Further, in the case of a lower alcohol, it may preferably be contained in an amount of from 0.10% by mass to 2.00% by mass, more preferably from 0.80% by mass to 1.20% by mass.

Think that these substances inhibit freedom by acting on hydrogen peroxide The base is generated while suppressing the decomposition of hydrogen peroxide. Further, when the phenyl urea is contained in an amount of more than 0.20% by mass based on the total amount of the etching liquid, the phenyl group and the hydrogen peroxide are reacted to produce a precipitate different from the reactant of the azole compound and hydrogen peroxide.

<chelating agent>

The decomposition of hydrogen peroxide is promoted by etching Cu or Mo and dissolving in the etching solution. It is considered that the chelating agent inhibits the decomposition of hydrogen peroxide by aligning metal ions such as Cu or Mo to prevent metal ions from coming into contact with hydrogen peroxide. Therefore, in the present specification, the chelating agent system is considered to be a hydrogen peroxide decomposition inhibitor.

As a chelating agent, it is suitable to use an aluminum carboxylate called EDTA, hydroxyethyliminodiacetic acid (HIDA), and ethyldiamine-N,N'-disuccinic acid (EDDS). Acid chelating agent. The chelating agent may preferably be contained in an amount of from 0.50% by mass to 1.00% by mass, more preferably from 0.60% by mass to 0.90% by mass, based on the total amount of the etching solution.

<polyether>

The polyether system can be an etching rate inhibitor for Cu. When the polyether is used, the taper angle of the etched profile is reduced, and therefore, the adjustment at the taper angle can be suitably utilized. In particular, in the state where sulfuric acid is used as the inorganic acid, the effect becomes large. As the polyether, polyethylene glycol (PEG) can be suitably used. The polyethylene glycol system may preferably be contained in an amount of from 0.10% by mass to 0.50% by mass, more preferably from 0.20% by mass to 0.40% by mass, based on the total amount of the etching solution.

<copper ion>

When the etching liquid of the present invention is etched to contain Cu ions or Mo ions, it is confirmed that the etching rate is changed by increasing the concentration of Cu ions. The operation of the etching apparatus adds and controls the etching concentrate or hydrogen peroxide water so that the change in the etching rate is accommodated within a certain allowable range. Therefore, even in the state of a new liquid, it is preferable to accommodate the allowable range. Therefore, Cu ions of a predetermined range can be contained in the etching liquid. Specifically, if the Cu ion is contained in an amount of 500 ppm to 7000 ppm, preferably 2,000 ppm to 4,000 ppm, based on the total amount of the etching liquid, it is easy to assume a change in the etching rate.

<Other>

In addition to these components, various additives which are generally used can be added to the etching liquid of the present invention in the range which does not impede water and etching performance. The water system is precisely processed for the purpose, so it is preferable that there is no foreign matter. If it is pure water or ultrapure water, it becomes ideal.

<pH value, temperature>

The etching solution of the present invention is preferably used in a pH of 2 to 5, more preferably in the range of 3 to 4.5. The etching solution of the present invention can be used between 18 ° C and 40 ° C. More preferably, it is 18 ° C to 35 ° C, and most preferably 20 ° C to 32 ° C.

<save>

In the etching solution of the present invention, hydrogen peroxide is used. Hydrogen peroxide decomposes on its own. Therefore, the etching solution contains a hydrogen peroxide decomposition inhibitor. However, hydrogen peroxide and other liquids can be stored separately at the time of storage. Further, a raw material of hydrogen peroxide, a copper ion-removing material (referred to as "etching liquid material"), and water may be mixed to prepare a solution of the etching liquid raw material. The solution can be in a lower ratio than the latter The water ratio of the etchant liquid shown in the embodiment is described.

A solution in which the etching liquid raw material and the etching liquid raw material of water are mixed is referred to as an "etching concentrate". The etching concentrate is only slightly less in volume than the etching liquid, and is therefore convenient for storage or transfer. In addition, in order to reduce the volume at the time of storage or transfer, it is possible to reduce the "etching high concentrate" of the water of the "etching concentrate". The etched high concentrate system is said to contain 20% to 70% water. The etch concentrate contains more than 70% water. Therefore, the etching liquid of the present invention can be completed by combining an etching concentrate and hydrogen peroxide water, and can also be completed by combining etching of a high concentration liquid, water, and hydrogen peroxide water.

<etching method>

The object of using the etching solution of the present invention is a multilayer film in which molybdenum is a lower layer and copper is an upper layer of a copper layer/molybdenum layer. The thickness of the lower molybdenum layer is thinner than the thickness of the upper layer of copper. When the thickness of the lower layer is t0 and the thickness of the upper layer is t1, the range of t0/t1 is in the range of 0.01 to 0.2. When the range of t0/t1 is out of the range and the Mo layer is excessively thick, the residue of the Mo layer is likely to occur, and conversely, when it is too thin, the function as the underlayer of the Cu layer cannot be exhibited.

Further, the substrate and the underlayer which form the molybdenum layer and the copper layer are not particularly limited, and may be IGZO (indium, gallium, zinc (Zinc), oxygen) including glass, germanium, and amorphous germanium. A metal oxide such as an amorphous semiconductor composed of (Oxide).

The etching solution of the present invention can be stored by storing hydrogen peroxide water, etching a high concentration liquid, and water (which may also be hydrogen peroxide water and an etching concentrate) during storage. So, in actual use, blend these And complete the etching solution. The method of blending is not limited if the concentration of the final hydrogen peroxide is a predetermined concentration.

When an example is shown, a certain amount of water is blended to mix the etching concentrate of the etching liquid material. Hydrogen peroxide is usually supplied as hydrogen peroxide water having a concentration higher than that of the etching solution of the present invention. Thus, hydrogen peroxide water and an etching concentrate are blended at each prescribed amount. This process can be referred to as a process for blending an etching solution for a multilayer film. Further, it is also possible to prepare an etching liquid by blending an etching high concentration liquid, water and hydrogen peroxide water having a concentration higher than that of the etching concentrate.

The copper ion is applied to any one of the stages of blending the etching concentrate (or etching the high concentration liquid) with the etching liquid material and water or by etching the concentrate and hydrogen peroxide water to align the etching liquid. It is also possible to mix copper ions. Of course, it is also possible to add copper ions after blending the etching solution. Further, in the state in which a sufficient etching concentrate and hydrogen peroxide water are additionally injected in the etching liquid which has been used, copper ions may not be added. Because of the presence of copper ions in the etchant.

At the time of etching, as described above, the etching liquid is used at a pH of 2 to 5 and 18 to 40 °C. Therefore, it is also preferable that the object to be processed to be etched is preheated to this temperature. The method of contacting the substrate with the etching liquid is not particularly limited. The method may be a shower type, starting from the top, and the etching liquid may be dispersed on the substrate to be processed, or may be a method of immersing the substrate to be processed in a treatment bath of the etching liquid. This process can be referred to as a process for contacting a substrate to be processed with an etching solution for a multilayer film.

Further, the substrate to be processed is formed on a substrate such as glass, and a molybdenum layer (Mo layer) and a copper layer (Cu layer) are laminated, and the film is formed to form a film. A substrate in a state in which the pattern of the resist layer is patterned.

[Examples]

<Explanation of various evaluation methods>

For the etching solution of the present invention, the etching rate (nm/min) of copper and molybdenum, the taper angle (°) of the wiring cross section of the etching, the molybdenum layer under the molybdenum layer, and the molybdenum layer remaining on the substrate (referred to as "Mo residue" The evaluation was carried out for items such as over-etching resistance, presence or absence of precipitates, and decomposition rate of hydrogen peroxide (% by mass/day).

The etching rate was measured as follows. First, a single-layer film was formed on the germanium wafer having a thermal oxide film of 100 nm by sputtering to a thickness of 300 nm of copper and 150 nm of molybdenum. The copper film and the molybdenum film were brought into contact with an etching solution of 30 ° C for 30 to 60 seconds (which also occurred in a state of 35 ° C according to a comparative example).

The resistance value of the film before and after the etching was measured using a 4-terminal 4-probe method resistivity meter (manufactured by Mitsubishi Chemical Corporation: MCP-T610 type) using a constant current application method. The change in film thickness was calculated from the change in the resistance value, and the etching rate was calculated.

The taper angle was measured as follows. First, a molybdenum layer was formed on a glass substrate by a sputtering method to a thickness of 20 nm, and a copper layer was formed thereon by a thickness of 300 nm to prepare a multilayer film sample of Cu/Mo. A resist patterned into a wiring shape was formed on the copper layer to form a substrate for evaluation of the taper angle. That is, the substrate for taper angle evaluation is composed of a substrate, a molybdenum layer and a copper layer thereon, and a patterned resist layer on the copper layer. The substrate for evaluating the taper angle is immersed in etching between the time of etching Liquid, etched. The sample after the etching was washed, and after drying, the wiring portion was cut and the cut surface was observed.

The observation of the cut surface was performed by using an SEM (Scanning Electron Microscope) (SU8020 type manufactured by Hitachi, Ltd.), and the cut surface was observed under the conditions of an acceleration voltage of 1 kV and 30,000 to 50,000 times. In addition, the etching is just the time from the start of etching until the film transmits light. The time point at which the film transmits light is confirmed by visual observation.

The shape of the cut surface is shown in Fig. 1. As shown in Fig. 1(a), the angle 5 formed by the substrate 1 and the etched inclined surface 6 is taken as the taper angle (°). If the taper angle is 30 to 60°, it is judged to be circular (○). If it is outside the range of the angle, it is judged to be a fork (×). In addition, "round" means success or pass, and "fork" means failure or failure. The evaluations below are also the same. Further, in Fig. 1(a), the Mo layer is indicated by the symbol 3, the Cu layer is indicated by the symbol 2, and the resist layer is indicated by the reference numeral 4.

The undercut of the molybdenum layer refers to a state in which the molybdenum layer 3 and the substrate 1 are further etched (reverse cone shape) as compared with the copper layer, as indicated by reference numeral 10 in Fig. 1(b). At the time of evaluation of the taper angle, evaluation can be performed simultaneously. If the cut under the molybdenum layer cannot be found by observation of 30,000 times to 50,000 times of the SEM, it is judged to be circular (○), and if it is found, it is judged to be forked (×).

The Mo residue was observed by an optical microscope and SEM. If the residue was confirmed, it was judged to be a fork (×), and if it was confirmed that there was no residue, it was judged to be circular (○). Further, the optical microscope was observed at a magnification of 100 times in bright field observation and dark field observation. Further, in the SEM, observation was performed by 30,000 times to 50,000 times.

The over-etching resistance (also referred to as "OE resistance resistance") is observed when the etching is performed twice as long as the etching time, the taper angle at the time of etching, the molybdenum layer undercut, and the Mo residue, if all are "circles" If it is evaluated, it is judged to be circular (○). If any one of the judgments is "fork", it becomes a fork (x).

The presence or absence of the precipitates is adjusted by placing the etchant liquid at room temperature for a predetermined period of time (several days), and it is judged by visual observation whether or not precipitates are generated in the bottle. In the state in which the precipitates are produced, the etching liquid is filtered by a filter paper, and the foreign matter remaining on the filter paper is washed with pure water, and dried at room temperature, by FT-IR (IR affinity, manufactured by Shimadzu Corporation) or SEM- The crystal or powder obtained by analysis of EDX (manufactured by Horiba, Ltd.). If the precipitate is not observed by visual observation, it is judged to be circular (○), and it is judged to be a fork (×) in a state of being confirmed by visual observation.

The etching liquid is important in that no precipitate is generated and the cross-sectional shape of the wiring is appropriate. However, in order to lengthen the life of the plating bath, the decomposition rate of hydrogen peroxide is also an important item. Here, the decomposition rate of hydrogen peroxide as a reference is also evaluated as an evaluation item.

The decomposition rate of hydrogen peroxide is potassium permanganate, and as a titration reagent, an automatic titrator (manufactured by Mitsubishi Chemical Corporation, GP-200) is used to measure immediately after the etching liquid is conditioned and after a predetermined time (about Hydrogen peroxide concentration after 24 hours). Next, the decomposition rate was calculated from the amount of change in the concentration of hydrogen peroxide.

If the amount of reduction in hydrogen peroxide concentration after 24 hours (day) is less than 1.0% by mass, it is evaluated as a circle (○), and if it is 1.0. When the mass is 100% or more, it is evaluated as a fork (×). Further, even if the decomposition rate of hydrogen peroxide is a fork (x), if the other item is a circle (○), it can be said to be the etching liquid of the present invention. In addition, all the evaluations were evaluated as a triangle (Δ) in a state in which the value of the circular (○) evaluation was not satisfied and the value was extremely close to the limit value.

(Example 1)

It will be composed of sulfuric acid: 0.06 mass%, glycolic acid: 2.50 mass%, aspartic acid: 0.44 mass%, glutamic acid: 0.87 mass%, beta alanine: 0.66 mass%, 1 amino 2 propanol: 1.61 mass %, phenyl urea: 0.11% by mass, ethylidene diamine tetraacetic acid (hereinafter, also referred to as "EDTA".): 0.88 mass% of the composition of the etching liquid, blended with water: 92.87 mass%, prepared etching Concentrate.

An etchant having a hydrogen peroxide concentration of 5.30% by mass was prepared by mixing 35% of hydrogen peroxide and etching the concentrate. Further, copper sulfate was added to prepare a copper ion concentration to be 2000 ppm. In addition, the liquid temperature was used at 30 °C. The results of the concentration of each component occupied by the entire etching solution and the respective evaluation items are shown in Table 1.

(Example 2)

It will be composed of sulfuric acid: 0.07 mass%, glycolic acid: 2.50 mass%, aspartic acid: 0.45% by mass, glutamic acid: 0.88 mass%, beta alanine: 0.66 mass%, and 1 amine 2 propanol: 1.61 mass %, phenyl urea: 0.11% by mass, ethylenediaminetetraacetic acid: 0.88 mass%, polyethylene glycol (hereinafter, also referred to as "PEG"): 0.33 mass% of the composition of the etching liquid, blended In water: 92.51% by mass, an etching concentrate was prepared.

Mix 35% hydrogen peroxide and etch concentrate to prepare hydrogen peroxide An etching solution having a concentration of 5.30% by mass. Further, copper sulfate was added to prepare a copper ion concentration to be 2000 ppm. In addition, the liquid temperature was used at 30 °C. The results of the concentration of each component occupied by the entire etching solution and the respective evaluation items are shown in Table 1.

(Example 3)

Nitric acid: 0.19% by mass, glycolic acid: 2.05% by mass, aspartic acid: 0.44% by mass, glutamic acid: 0.90% by mass, β-alanine: 0.66% by mass, 1 amino 2-propanol: 1.94% by mass %, phenylurea: 0.11% by mass, and an ethylene diamine tetraacetic acid: 0.87 mass% of an etchant raw material, which was mixed with water: 92.84% by mass to prepare an etching concentrate.

An etchant having a hydrogen peroxide concentration of 5.30% by mass was prepared by mixing 35% of hydrogen peroxide and etching the concentrate. Further, copper sulfate was added to prepare a copper ion concentration to be 2000 ppm. In addition, the liquid temperature was used at 30 °C. The results of the concentration of each component occupied by the entire etching solution and the respective evaluation items are shown in Table 1.

(Example 4)

Nitric acid: 0.18 mass%, glycolic acid: 2.55 mass%, aspartic acid: 0.45% by mass, glutamic acid: 0.91% by mass, β alanine: 0.69% by mass, 1 amino 2 propanol: 1.66 mass %, phenylurea: 0.11% by mass, 1-propanol: 1.20% by mass of the composition of the etching liquid, which was mixed with water: 92.25% by mass to prepare an etching concentrate.

An etchant having a hydrogen peroxide concentration of 5.30% by mass was prepared by mixing 35% of hydrogen peroxide and etching the concentrate. Further, copper sulfate was added to prepare a copper ion concentration to be 2000 ppm. In addition, the liquid temperature was used at 30 °C. The results of the concentration of each component occupied by the entire etching solution and the respective evaluation items are shown in Table 1.

(Example 5)

It will be: sulfuric acid: 0.05% by mass, glycolic acid: 2.47% by mass, aspartic acid: 0.44% by mass, glutamic acid: 0.87% by mass, glycine: 1.17% by mass, 1 amino 2 propanol: 1.61 mass %, phenylurea: 0.11% by mass, and ethyldiaminetetraacetic acid: 0.87 mass%, and the composition of the etching liquid was adjusted to water: 92.41% by mass to prepare an etching concentrate.

An etchant having a hydrogen peroxide concentration of 5.30% by mass was prepared by mixing 35% of hydrogen peroxide and etching the concentrate. Further, copper sulfate was added to prepare a copper ion concentration to be 2000 ppm. In addition, the liquid temperature was used at 30 °C. The results of the concentration of each component occupied by the entire etching solution and the respective evaluation items are shown in Table 1.

(Example 6)

It will be composed of sulfuric acid: 0.07 mass%, glycolic acid: 2.46 mass%, aspartic acid: 0.44 mass%, glutamic acid: 0.87 mass%, beta alanine: 1.74 mass%, 1 amino 2 propanol: 1.58 mass %, phenylurea: 0.11% by mass of the composition of the etching liquid, adjusted to water: 92.73% by mass, to prepare an etching concentrate.

An etchant having a hydrogen peroxide concentration of 5.30% by mass was prepared by mixing 35% of hydrogen peroxide and etching the concentrate. Further, copper sulfate was added to prepare a copper ion concentration to be 2000 ppm. In addition, the liquid temperature was used at 30 °C. The results of the concentration of each component occupied by the entire etching solution and the respective evaluation items are shown in Table 1.

(Example 7)

An etching liquid raw material composed of sulfuric acid: 0.07 mass%, glycolic acid: 2.50 mass%, citric acid: 0.61 mass%, 1 amino 2 propanol: 1.58 mass%, and phenyl urea: 0.11 mass% was blended in Water: 95.13% by mass, modulating the etching concentrate.

An etchant having a hydrogen peroxide concentration of 5.30% by mass was prepared by mixing 35% of hydrogen peroxide and etching the concentrate. Further, copper sulfate was added to prepare a copper ion concentration to be 2000 ppm. In addition, the liquid temperature was used at 30 °C. The results of the concentration of each component occupied by the entire etching solution and the respective evaluation items are shown in Table 1.

(Example 8)

It is composed of sulfuric acid: 0.07 mass%, glycolic acid: 2.27 mass%, beta alanine: 0.66 mass%, 1 amino 2 propanol: 1.94 mass%, phenyl urea: 0.11 mass%, and ethylidene diamine tetraacetate An etching liquid raw material having a composition of 0.87 mass% and polyether: 0.34 mass% was blended in water: 93.74 mass% to prepare an etching concentrate.

An etchant having a hydrogen peroxide concentration of 5.30% by mass was prepared by mixing 35% of hydrogen peroxide and etching the concentrate. Further, copper sulfate was added to prepare a copper ion concentration to be 2000 ppm. In addition, the liquid temperature was used at 30 °C. The results of the concentration of each component occupied by the entire etching solution and the respective evaluation items are shown in Table 1.

<Comparative example using an azole compound>

(Comparative Example 1)

It is composed of glycolic acid: 5.62 mass%, glycine: 5.20 mass%, 1 amino 2 propanol: 1.31 mass%, phenyl urea: 0.11 mass%, and 5 amine 1H tetrazole: 0.13 mass%. The etching liquid raw material was blended in water: 87.63 mass%, and an etching concentrate was prepared.

An etchant having a hydrogen peroxide concentration of 5.30% by mass was prepared by mixing 35% of hydrogen peroxide and etching the concentrate. Further, copper sulfate was added to prepare a copper ion concentration to be 2000 ppm. In addition, the liquid temperature was used at 35 °C. The results of the respective component concentrations occupied by the entire etching solution and the respective evaluation items are shown in Table 2.

(Comparative Example 2)

Etching liquid raw material composed of nitric acid: 3.91 mass%, glycine acid: 4.33 mass%, 1 amino group 2 propanol: 3.86 mass%, phenyl urea: 0.11 mass%, and 5 amine group 1H tetrazole: 0.11 mass% , blended with water: 87.68 mass%, prepared etching concentrate.

An etchant having a hydrogen peroxide concentration of 5.30% by mass was prepared by mixing 35% of hydrogen peroxide and etching the concentrate. Further, copper sulfate was added to prepare a copper ion concentration to be 2000 ppm. In addition, the liquid temperature was used at 35 °C. The results of the respective component concentrations occupied by the entire etching solution and the respective evaluation items are shown in Table 2.

(Comparative Example 3)

It is composed of glycolic acid: 2.42% by mass, glycine: 1.25 mass%, 1 amino 2 propanol: 0.67 mass%, phenyl urea: 0.12 mass%, and 5 amine 1H tetrazole: 0.09 mass%. The etching liquid raw material was blended in water: 95.45 mass%, and an etching concentrate was prepared.

An etchant having a hydrogen peroxide concentration of 5.30% by mass was prepared by mixing 35% of hydrogen peroxide and etching the concentrate. Further, copper sulfate was added to prepare a copper ion concentration to be 2000 ppm. In addition, the liquid temperature was used at 35 °C. The results of the respective component concentrations occupied by the entire etching solution and the respective evaluation items are shown in Table 2.

(Comparative Example 4)

Glycolic acid: 2.65 mass%, glycine acid: 1.00 mass%, beta alanine: 0.82 mass%, 1 amine 2 propanol: 0.39 mass%, phenyl urea: 0.12 mass%, 5 amine group 1H four Azole: 0.12% by mass of an etchant raw material, which was mixed with water: 94.90% by mass to prepare an etching concentrate.

Mix 35% hydrogen peroxide and etch concentrate to prepare hydrogen peroxide An etching solution having a concentration of 5.30% by mass. Further, copper sulfate was added to prepare a copper ion concentration to be 2000 ppm. In addition, the liquid temperature was used at 35 °C. The results of the respective component concentrations occupied by the entire etching solution and the respective evaluation items are shown in Table 2.

(Comparative Example 5)

An etching liquid raw material composed of nitric acid: 0.12% by mass, citric acid: 2.45% by mass, 1 amino 2 propanol: 2.62% by mass, phenyl urea: 0.08% by mass, and 5 amine 1H tetrazole: 0.29% by mass. Blended to water: 94.44% by mass to prepare an etching concentrate.

An etchant having a hydrogen peroxide concentration of 5.30% by mass was prepared by mixing 35% of hydrogen peroxide and etching the concentrate. Further, copper sulfate was added to prepare a copper ion concentration to be 2000 ppm. In addition, the liquid temperature was used at 35 °C. The results of the respective component concentrations occupied by the entire etching solution and the respective evaluation items are shown in Table 2.

(Comparative Example 6)

Nitric acid: 0.08 mass%, glycolic acid: 2.20 mass%, malonic acid: 3.98 mass%, lactic acid: 1.01 mass%, 1 amino 2 propanol: 2.64 mass%, phenyl urea: 0.12 mass%, 5 Amino 1H tetrazole: 0.14% by mass of an etching liquid raw material, and was mixed with water: 89.83 mass% to prepare an etching concentrate.

An etchant having a hydrogen peroxide concentration of 5.30% by mass was prepared by mixing 35% of hydrogen peroxide and etching the concentrate. Further, copper sulfate was added to prepare a copper ion concentration to be 2000 ppm. In addition, the liquid temperature was used at 35 °C. The results of the respective component concentrations occupied by the entire etching solution and the respective evaluation items are shown in Table 2.

<Comparative example of no azole compound used>

(Comparative Example 7)

An etching liquid raw material composed of glycolic acid: 2.65 mass%, lactic acid: 1.00 mass%, 1 amino 2 propanol: 2.52 mass%, and phenyl urea: 0.11 mass% was blended in water: 93.72 mass%, prepared Etching the concentrate.

An etchant having a hydrogen peroxide concentration of 5.30% by mass was prepared by mixing 35% of hydrogen peroxide and etching the concentrate. Further, copper sulfate was added to prepare a copper ion concentration to be 2000 ppm. In addition, the liquid temperature was used at 35 °C. Table 3 shows the results of the concentration of each component occupied by the entire etching solution and the evaluation items.

(Comparative Example 8)

The etching liquid raw material composed of malonic acid: 3.54% by mass, glycine: 1.40% by mass, 1 amino 2 propanol: 1.64% by mass, and phenyl urea: 0.11% by mass was blended in water: 93.31% by mass, The etching concentrate is prepared.

An etchant having a hydrogen peroxide concentration of 5.30% by mass was prepared by mixing 35% of hydrogen peroxide and etching the concentrate. Further, copper sulfate was added to prepare a copper ion concentration to be 2000 ppm. In addition, the liquid temperature was used at 35 °C. Table 3 shows the results of the concentration of each component occupied by the entire etching solution and the evaluation items.

(Comparative Example 9)

An etching liquid raw material composed of citric acid: 3.61% by mass, glycine: 1.43% by mass, 1 amino 2 propanol: 1.64% by mass, and phenyl urea: 0.11% by mass, adjusted to water: 93.21% by mass, prepared Etching the concentrate.

An etchant having a hydrogen peroxide concentration of 5.30% by mass was prepared by mixing 35% of hydrogen peroxide and etching the concentrate. Further, copper sulfate was added to prepare a copper ion concentration to be 2000 ppm. In addition, the liquid temperature was used at 35 °C. Table 3 shows the results of the concentration of each component occupied by the entire etching solution and the evaluation items.

(Comparative Example 10)

The etching liquid raw material composed of lactic acid: 4.73 mass%, glycine: 1.39 mass%, 1 amino 2 propanol: 1.72 mass%, and phenyl urea: 0.11 mass% was blended in water: 92.05% by mass, and etched. Concentrate.

An etchant having a hydrogen peroxide concentration of 5.30% by mass was prepared by mixing 35% of hydrogen peroxide and etching the concentrate. Further, copper sulfate was added to prepare a copper ion concentration to be 2000 ppm. In addition, the liquid temperature was used at 35 °C. Table 3 shows the results of the concentration of each component occupied by the entire etching solution and the evaluation items.

(Comparative Example 11)

An etching liquid raw material composed of glycolic acid: 2.80% by mass, glycine: 1.41% by mass, 1 amino 2 propanol: 1.25 mass%, and phenyl urea: 0.11% by mass, adjusted to water: 94.43 mass% , modulating the etching concentrate.

An etchant having a hydrogen peroxide concentration of 5.30% by mass was prepared by mixing 35% of hydrogen peroxide and etching the concentrate. Further, copper sulfate was added to prepare a copper ion concentration to be 2000 ppm. In addition, the liquid temperature was used at 35 °C. Table 3 shows the results of the concentration of each component occupied by the entire etching solution and the evaluation items.

<Result>

Examples 1 to 8 are etching solutions of the present invention. Since there is no azole-containing compound, no reactants and no precipitates are formed between the hydrogen peroxide and the hydrogen peroxide. In the acidic organic acid, three kinds of glycolic acid, aspartic acid and glutamic acid are used at the same time. Even among these, EDTA or 1 propanol is still used. (Examples 1 to 5) In addition to the absence of precipitates, any one of the taper angle, Mo undercut, Mo residue, and O.E. resistance was also evaluated as a circular (○). Further, the rate of decomposition of hydrogen peroxide is also less than 0.1% by mass/day, and a desired result can be obtained.

Further, since the over-etch resistance is good, etching can be performed by maintaining a good taper angle twice as long as the time just after the etching is started. Further, the etching liquids of these embodiments have a film thickness ratio (t0/t1) of Mo and Cu different from the state of the embodiment (20/300), and if the film thickness ratio is between 0.01 and 0.2, A taper angle of 30° to 60° can also be achieved.

In Example 6, a neutral organic acid was substituted with glycine to form beta alanine compared to Example 5, without the addition of EDTA. When EDTA is removed, the decomposition rate (% by mass/day) of hydrogen peroxide is more than 1.0% by mass/day. However, the cross-sectional shape of the etched wiring is good.

Examples 7 and 8 can use ethylene glycol acid and citric acid or glycolic acid and beta alanine to adjust the etching rate of Cu and Mo, and form a taper angle in an appropriate range. However, the decomposition rate of hydrogen peroxide is somewhat more than 1.0% by mass/day. From these, the etching liquid of the present invention can be said to contain at least glycolic acid as an organic acid, and has hydrogen peroxide, an inorganic acid, an amine compound, and a hydrogen peroxide stabilizer. In addition, a chelating agent may also be included.

Comparative Examples 1 to 6 are examples in which an azole compound is contained. As the azole compound, 5-amino-1H tetrazole was used. As an effect of using an azole compound, the etching rate of Cu can be suppressed, and the etching rate of Mo can be increased. Therefore, the taper angle can be controlled by obtaining a balance with the inorganic acid.

Comparative Examples 1 to 5 increase the etching rate of Mo and increase the taper angle. In Comparative Example 6, only the etching rate of copper was increased by a well-adjusted composition, and therefore, a mixture of glycolic acid, malonic acid, and lactic acid was used. In Comparative Example 6, the taper angle system gave appropriate results. However, when the etching speed of Mo is also very rapid and excessive etching is performed, only a slight Mo layer is cut.

In Comparative Example 1 to Comparative Example 6, the composition of the taper angle can be adjusted as described above, but the azole compound and the hydrogen peroxide system react to generate precipitates.

Comparative Examples 7 to 11 are examples in which no azole compound is contained. As shown in Comparative Example 1 to Comparative Example 6, the etching rates of Cu and Mo can be adjusted by a combination of a mineral acid and an azole compound. In Comparative Example 7 to Comparative Example 11, it was attempted to adjust the etching rates of Cu and Mo by adjusting the organic acid and the amine in a state in which no azole compound was used. The amine system uses 1 amino 2-propanol.

In Comparative Example 7, glycolic acid and lactic acid were used as the organic acid system, but the taper angle was small. In Comparative Example 8, malonic acid and glycine were used, but the etching rate of Cu was excessively high, and there was no residual film. In Comparative Example 9 to Comparative Example 11, the types of the neutral organic acid and the acidic organic acid were also changed. However, the etching rate of Cu was high, and the tapered angle system could not obtain a good shape. However, no azole compound was contained, and therefore no precipitate was produced.

EXAMPLES As evidenced by Comparative Example 7 to Comparative Example 11, since no azole compound was used, no precipitate was produced. Further, when compared with Comparative Example 7 to Comparative Example 11, it was possible to adjust by using either glycolic acid, aspartic acid, and glutamic acid, using either EDTA or a lower alcohol of 1-propanol. The ratio of the etching speed of Cu and Mo is such that an appropriate cross-sectional shape of the etching portion is obtained, and there is no precipitate, and the etching liquid having a long plating bath life is also obtained.

[Industrial Availability]

The etching liquid of the present invention may be formed on a substrate such as a glass substrate, a germanium substrate, an amorphous germanium substrate, a metal oxide substrate, or the like, regardless of the products of the FPD such as a liquid crystal display, a plasma display, or an organic EL. A wiring layer on which a molybdenum layer and a copper layer are laminated on a base layer composed of these materials is widely used.

Claims (6)

An etching solution for a multilayer film comprising a copper layer and a molybdenum layer, comprising: hydrogen peroxide; an inorganic acid which is at least one of sulfuric acid or nitric acid; and an acidic organic acid which is derived from glycolic acid and aspartic acid The amine acid, glutamic acid, and citric acid contain at least one or more of glycolic acid; a neutral organic acid which is any one of glycine and beta alanine; and an amine compound which is 1-amino -2-propanol; and a hydrogen peroxide decomposition inhibitor, which is a phenyl urea or a lower alcohol; wherein the hydrogen peroxide is 3.50% by mass to 5.80% by mass of the total amount of the etching solution, and the inorganic acid is relative to the etching solution The total amount is 0.01% by mass to 0.50% by mass, the acidic organic acid is 1% by mass to 7% by mass based on the total amount of the etching liquid, and the neutral organic acid is 0.10% by mass to 3.00% by mass based on the total amount of the etching liquid. The amine compound is 0.50% by mass to 2.00% by mass based on the total amount of the etching solution, and the hydrogen peroxide decomposition inhibitor is 0.05% by mass to 0.20% by mass based on the total amount of the etching solution, and the pH of the etching solution is 2 ~5, and does not contain azole compounds, phosphorus compounds and fluorine Compounds. Etching of a multilayer film including a copper layer and a molybdenum layer as in the first application of the patent scope a liquid, which further comprises an aminocarboxylic acid-based chelating agent, which is an ethylenediaminetetraacetic acid (EDTA), hydroxyethyliminodiacetic acid (HIDA), and an ethylenediamine-N,N' Any one of disuccinic acid (EDDS) is contained in an amount of 0.50% by mass to 1.00% by mass based on the total amount of the etching solution. An etching solution for a multilayer film comprising a copper layer and a molybdenum layer according to claim 1 or 2, further comprising polyethylene glycol, which is contained in an amount of 0.10% by mass to 0.50% by mass based on the total amount of the etching solution. The etching solution for a multilayer film comprising a copper layer and a molybdenum layer according to any one of claims 1 to 3, further comprising 500 to 7000 ppm of copper ions. An etching concentrate for a multilayer film comprising a copper layer and a molybdenum layer, comprising: a mineral acid which is at least one of sulfuric acid or nitric acid; and an acidic organic acid which is derived from glycolic acid, aspartic acid, The glutamic acid and the citric acid contain at least one or a plurality of glycolic acids; the neutral organic acid, which is any one of glycine and beta alanine; and the amine compound, which is 1-amino-2- a propane alcohol; a hydrogen peroxide decomposition inhibitor which is a phenyl urea or a lower alcohol; and water, wherein the total amount of the etching liquid is mixed with water in a manner of from 3.50% by mass to 5.80% by mass of hydrogen peroxide. The acid is from 0.01% by mass to 0.50% by mass, the acidic organic acid is from 1% by mass to 7% by mass, the neutral organic acid is from 0.10% by mass to 3.00% by mass, and the amine compound is from 0.50% by mass to 2.00% by mass. The aforementioned hydrogen peroxide decomposition inhibitor is 0.05% by mass to 0.20% by mass, and does not contain an azole compound, a phosphorus compound, and a fluorine compound. An etching method for a multilayer film comprising a copper layer and a molybdenum layer, comprising: comprising at least one of a mineral acid which is sulfuric acid or nitric acid; an acidic organic acid which is derived from glycolic acid and aspartic acid , glutamic acid, citric acid containing at least one or a plurality of glycolic acids; a neutral organic acid, which is any one of glycine and beta alanine; an amine compound, which is 1-amino-2 -propanol; a hydrogen peroxide decomposition inhibitor which is a phenyl urea or a lower alcohol; and water, wherein the total amount of the etching liquid when mixed with water in a manner of from 3.50% by mass to 5.80% by mass of hydrogen peroxide, the foregoing The inorganic acid is 0.01% by mass to 0.50% by mass, the acidic organic acid is 1% by mass to 7% by mass, the neutral organic acid is 0.10% by mass to 3.00% by mass, and the amine compound is 0.50% by mass to 2.00% by mass. In the etching concentrate containing 0.05% by mass to 0.20% by mass of the hydrogen peroxide decomposition inhibitor and not containing the azole compound, the phosphorus compound, and the fluorine compound, the total amount of the etching solution is 3.50% by mass to 5.80% by mass based on the total amount of the etching solution. Hydrogen peroxide and water are blended to blend more The film used was an etching process; and, the multilayer film such that the etching solution, the process contacts the substrate to be processed, the multilayer film in an etching solution to come into contact with the treatment process of the substrate, for The etching liquid for a multilayer film has a pH of 2 to 5 and a liquid temperature of 18 to 35 °C.