JPWO2015075765A1 - Etching solution for multilayer film, etching concentrated solution, and etching method - Google Patents

Abstract

In an etchant that etches a multilayer film of a copper layer and a molybdenum layer with a single solution, the cross-sectional shape of the edge after etching is deposited in the etchant with a geometrical requirement that there is no undercut and a forward taper. It is important that no product is generated when used in mass production. Etching solution for multilayer film containing hydrogen peroxide, inorganic acid, acidic organic acid, neutral organic acid, amine compound, copper layer containing hydrogen peroxide decomposition inhibitor and molybdenum layer contains azole compound Therefore, no reaction product is generated with hydrogen peroxide, and no precipitate is generated in the etching solution. In addition, the cross-sectional shape of the edge after etching can be a preferable forward tapered shape. Furthermore, since it does not contain phosphorus compounds or fluorine compounds, it has a light environmental impact during disposal.

Description

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

  Aluminum has been used as a wiring material for TFTs (Thin Film Transistors) of flat panel displays (FPD) such as liquid crystal and organic EL (Electro-Luminescence). In recent years, large-screen, high-definition FPDs have become widespread, and the wiring material used has been required to have a resistance lower than that of aluminum. In recent years, therefore, copper, which has a lower resistance than aluminum, has been used as a wiring material.

  When copper is used as a wiring material, there are two problems, that is, adhesion between the substrate and diffusion into the semiconductor substrate. That is, in the case of using the gate wiring, there is a case where the adhesive force between the substrates such as glass is not sufficient even when the sputtering method that has a relatively high collision energy to the base material is used. In addition, when used for source / drain wiring, there arises a problem that the deposited copper diffuses into the underlying silicon and changes the electrical design value of the semiconductor.

  In order to solve this problem, a multilayer structure in which a molybdenum layer is first formed on a substrate or a semiconductor substrate and a copper layer is formed thereon is currently employed.

The FPD wiring is formed by wet etching a multilayer film formed by a sputtering method. This is because a large area can be formed at a stretch, and the process can be shortened. Here, the following points are important for wet etching of wiring.
(1) Processing accuracy is high and uniform.
(2) The wiring cross section after processing is a forward taper of a predetermined angle.
(3) Etching performance is unlikely to deteriorate due to copper ions contained in the etching solution (long bath life).
(4) There is little generation of precipitates.

  The first item, high processing accuracy and uniformity, is an essential item when processing not only wet etching but also a minute region. The shape of the wiring cross section, which is the second item, is a shape necessary for performing reliable wiring formation when forming large-area FPD wirings at once. This is because, if the etched edge portion of the multilayer film of the copper layer and the molybdenum layer is formed with a forward taper of 30 to 60 degrees from the substrate, an etching failure occurs, and the etching rate of copper and molybdenum This is because a margin for ensuring product quality can be secured even if the balance is different.

  The third item is the life problem of the etching solution itself. In order to etch a large area substrate, a large amount of etching solution is required. These etching solutions are circulated from the viewpoint of cost. The cost is lower when the period (life) in which the etching performance can be maintained is as long as possible.

  The fourth item is not only a problem for maintaining the etching apparatus, but also a problem related to the quality problem of the product. When precipitates are generated by etching, the piping of the etching apparatus may be clogged, or the holes of the shower nozzle for spraying the etching solution may be clogged. These phenomena cause the operation of the etching apparatus to stop, leading to an increase in cost. In addition, if the deposit adheres to the product via the etching solution, it causes a short circuit or disconnection, which directly affects the quality of the product.

  Regarding an etching solution for a multilayer film of a copper layer and a molybdenum layer, there is a report of an etching solution containing hydrogen peroxide and at least one selected from a neutral salt and an organic acid (Patent Document 1: Japanese Patent Application Laid-Open No. 2002-302780). (Japanese Patent No. 4282927).

  Further, hydrogen peroxide, an organic acid, a phosphate, a water-soluble cyclic amine compound as a first additive, and a water-soluble compound containing one of an amino group and a carboxyl group as a second additive, An etching solution of a copper molybdenum film containing a predetermined amount of each of a fluorine compound and deionized water has been reported (Patent Document 2: Japanese Patent Application Laid-Open No. 2004-193620 (Patent Document 4448322)).

  In addition, there is a report of an etching solution for molybdenum / copper / molybdenum nitride multilayer film containing hydrogen peroxide, organic acid, triazole compound, fluorine compound, and ultrapure water (Patent Document 3: Japanese Patent Laid-Open No. 2007-2007). No. 005790 (Patent No. 5111790)).

  Furthermore, (A) hydrogen peroxide, (B) an inorganic acid not containing a fluorine atom, (C) an organic acid that is at least one selected from succinic acid, glycolic acid, lactic acid, malonic acid, and malic acid, (D) carbon An amine compound having a number 2 to 10 and an amino group and a hydroxyl group so that the total number of groups is 2 or more, (E) 5-amino-1H-tetrazole, and (F) a hydrogen peroxide stabilizer An etching solution for a multilayer thin film containing a copper layer and a molybdenum layer having a pH of 2.5 to 5 has been reported (Patent Document 4: Japanese Patent No. 5051323).

JP 2002-302780 A (Patent No. 4282927) JP 2004-193620 A (Patent No. 4448322) JP 2007-005790 A (Patent No. 5111790) Japanese Patent No. 5051323

  Patent Document 1 discloses a specific etching solution in the case of a mixed solution of hydrogen peroxide and an organic acid, only that the copper and molybdenum can be etched simultaneously by adjusting the ratio of hydrogen peroxide. The composition of is not disclosed at all.

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

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

  Further, when a phosphorus compound or a fluorine compound is used as a component of the etching solution, the performance as the etching solution is easily obtained, but the burden on the environment is increased during disposal.

  The present invention has been conceived in view of the above-described problems, and is an etching solution composition for a multilayer film including a copper layer and a molybdenum layer that satisfies the point important for wet etching of wiring described in [Background Art]. Is to provide. In particular, the present invention provides an etching solution, a concentrated solution thereof, and an etching method that do not generate precipitates in the etching solution and that do not increase the environmental load during disposal.

More specifically, an etching solution for a multilayer film including a copper layer and a molybdenum layer according to the present invention,
Hydrogen peroxide,
Inorganic acids,
An acidic organic acid,
Neutral organic acids,
An amine compound;
It contains hydrogen peroxide decomposition inhibitor.

Moreover, the etching liquid which concerns on this invention can be comprised in the state of a concentrate so that it may not become bulky at the time of a preservation | save or a transfer. More specifically, an etching concentrate for a multilayer film comprising a copper layer and a molybdenum layer according to the present invention,
Inorganic acids,
An acidic organic acid,
Neutral organic acids,
An amine compound;
A hydrogen peroxide decomposition inhibitor;
It contains water.

In addition, the etching method for multilayer film including the copper layer molybdenum layer according to the present invention,
Inorganic acids,
An acidic organic acid,
Neutral organic acids,
An amine compound;
A step of preparing an etching solution for multilayer film by preparing an etching concentrate containing hydrogen peroxide decomposition inhibitor and water, water and hydrogen peroxide;
The method includes a step of bringing the multilayer film etching solution into contact with a substrate to be processed.

  In the etching solution according to the present invention, the cross-sectional shape of the etched wiring becomes a forward taper, and the shape is maintained even when overetching is performed. Moreover, since it is a structure which does not contain the azole compound which produces | generates a precipitate, when it uses with hydrogen peroxide, there will be no generation | occurrence | production of a precipitate in an etching liquid, and malfunctions, such as piping clogging and a clogging of a shower nozzle, will not generate | occur | produce. Therefore, it is not necessary to stop the operation of the etching apparatus due to the generation of precipitates, and stable production is possible.

  In addition, the etching concentrate according to the present invention does not contain hydrogen peroxide and a predetermined amount of water from the above etching solution, and therefore it can be stored or transported without being bulky and causing little change over time. In addition, since the etching concentrate and hydrogen peroxide can be handled separately, it is possible to easily adjust the concentration of the etching liquid whose component concentration has changed due to use.

  Further, the etching method according to the present invention prepares an etching solution having a stable composition at any time because the etching concentrated solution and the hydrogen peroxide solution are prepared and the etching solution is prepared and brought into contact with the substrate to be processed. In addition, the cross section of the formed wiring has a forward taper, and even when overetching, the taper angle can be etched while maintaining a suitable angle range.

  Moreover, since the etching solution according to the present invention does not contain substances such as phosphorus compounds, chlorine compounds, and fluorine compounds, there is an advantage that the burden on the environment is light when discarded.

It is a conceptual diagram showing the cross section of the wiring formed by the etching.

  The etching solution according to the present invention will be described below. The following description shows an embodiment of the etching solution according to the present invention, and the following embodiments and examples may be modified without departing from the spirit of the present invention. The etching solution according to the present invention is characterized in that no precipitate is generated in the etching solution. As shown in the examples described later, it was strongly suggested that the cause of the precipitate was a reaction product of an azole compound and hydrogen peroxide. Therefore, the etching solution according to the present invention does not contain an azole compound.

  Moreover, in order to reduce environmental load, a phosphorus compound, a fluorine compound, and a chlorine compound are not included. However, it may be included when it does not affect the etching performance and product quality, or when the environmental load at the time of disposal is below the standard established in each country. Further, such an amount may be interpreted as not including.

<Hydrogen peroxide>
In the etching of copper, copper is oxidized to become copper oxide (CuO), which is dissolved by an inorganic acid. In addition, the etching of molybdenum is oxidized to molybdenum oxide (MoO3) and is dissolved in water. Hydrogen peroxide is used as an oxidizing agent that oxidizes copper and molybdenum. Hydrogen peroxide is preferably 3.50% by mass to 5.80% by mass of the total amount of the etching solution. Hydrogen peroxide is also called “overwater”.

<Inorganic acid>
Inorganic acids are used to dissolve oxidized copper. Phosphorus compounds and fluorine compounds are not used in order not to affect the substrate material such as glass or silicon and to reduce the environmental load when discarding the etchant. Also, hydrochloric acid is not used. Nitric acid and sulfuric acid can be suitably used. The inorganic acid is included in the range of 0.01% to 0.50% by weight, preferably 0.02% to 0.20% by weight, based on the total amount of the etching solution.

<Organic acid>
The organic acid component mainly serves to adjust the taper angle of the cross section of the etched wiring. It is also considered to have a function to suppress the decomposition of hydrogen peroxide to some extent. As the organic acid component, a combination of an acidic organic acid and a neutral organic acid is used. Moreover, you may combine both an acidic organic acid and a neutral organic acid.

  Preferred examples of the organic acid that can be used include aliphatic carboxylic acids having 1 to 18 carbon atoms and aromatic carboxylic acids having 6 to 10 carbon atoms, and amino acids having 1 to 10 carbon atoms.

  Examples of the aliphatic carboxylic acid having 1 to 18 carbon atoms include 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, valeric acid, glutaric acid, itaconic acid, adipic acid, caproic acid, adipic acid, citric acid, propanetricarboxylic acid, trans-aconitic acid, enanthic acid, caprylic acid, lauric acid, myristic acid, palmitic acid, stearin Preferred are acid, oleic acid, linoleic acid, linolenic acid and the like.

  Preferred examples of the aromatic carboxylic acid having 6 to 10 carbon atoms include benzoic acid, salicylic acid, mandelic acid, phthalic acid, isophthalic acid, and terephthalic acid.

  Examples of the amino acid having 1 to 10 carbon atoms include carbamic acid, alanine, glycine, asparagine, aspartic acid, sarcosine, serine, glutamine, glutamic acid, 4-aminobutyric acid, iminodibutyric acid, arginine, leucine, isoleucine, nitrilotriacetic acid, etc. Is preferred.

  Among the above organic acids, glycolic acid, aspartic acid, glutamic acid, and citric acid can be suitably used as the acidic organic acid. In particular, glycolic acid, aspartic acid, and glutamic acid can obtain suitable characteristics by simultaneously using three kinds. In addition, it is preferable to contain 1 to 7 mass% of acidic organic acids with respect to the etching liquid whole quantity.

  When glycolic acid, aspartic acid and glutamic acid are used at the same time, glycolic acid is preferably contained in an amount of 1% by mass to 5% by mass, more preferably 1.50% by mass to 2.50% by mass with respect to the total amount of the etching solution. It is good to let them. Further, aspartic acid is preferably contained in an amount of 0.10% by mass to 1.00% by mass, more preferably 0.20% by mass to 0.50% by mass with respect to the total amount of the etching solution. Further, glutamic acid is preferably contained in an amount of 0.1 to 1.0% by mass, more preferably 0.60 to 0.90% by mass with respect to the total amount of the etching solution.

  Moreover, glycine, alanine, or β-alanine can be suitably used as the neutral organic acid. Further, the neutral organic acid is preferably contained in an amount of 0.10% by mass to 3.00% by mass with respect to the total amount of the etching solution.

  In addition to the above, glycolic acid and one kind of other acidic organic acid or one kind of neutral organic acid may be combined. In that case, glycolic acid is preferably contained in an amount of 1% by mass to 5% by mass, and more preferably 1.50% by mass to 2.30% by mass with respect to the total amount of the etching solution. On the other hand, the acidic organic acid or neutral organic acid is preferably 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 with respect to the total amount of the etching solution. Is good.

<Amine compound>
The amine compound is mainly responsible for adjusting the pH of the etching solution. As an amine compound, a C2-C10 thing can be utilized suitably. More specifically, ethylenediamine, trimethylenediamine, tetramethylenediamine, 1,2-propanediamine, 1,3-propanediamine, N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1 , 3-propanediamine, 1,3-diaminobutane, 2,3-diaminobutane, pentamethylenediamine, 2,4-diaminopentane, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, N-methyl Ethylenediamine, N, N-dimethylethylenediamine, trimethylethylenediamine, N-ethylethylenediamine, N, N-diethylethylenediamine, triethylethylenediamine, 1,2,3-triaminopropane, hydrazine, tris (2-aminoethyl) amino , Tetra (aminomethyl) methane, diethylenetriamine, triethylenetetramine, tetraethylpentamine, heptaethyleneoctamine, nonaethylenedecamine, diazabicycloundecene, etc .; ethanolamine, N-methylethanolamine, N-methyldiethanolamine N-ethylethanolamine, N-aminoethylethanolamine, N-propylethanolamine, N-butylethanolamine, diethanolamine, triethanolamine, 1-amino-2-propanol, N-methylisopropanolamine, N-ethylisopropanol Amine, N-propylisopropanolamine, 2-aminopropan-1-ol, N-methyl-2-amino-propan-1-ol, N-ethyl-2-amino Propan-1-ol, 1-aminopropan-3-ol, N-methyl-1-aminopropan-3-ol, N-ethyl-1-aminopropan-3-ol, 1-aminobutan-2-ol, N -Methyl-1-aminobutan-2-ol, N-ethyl-1-aminobutane-2-ol, 2-aminobutan-1-ol, N-methyl-2-aminobutan-1-ol, N-ethyl-2-aminobutane- 1-ol, 3-aminobutan-1-ol, N-methyl-3-aminobutan-1-ol, N-ethyl-3-aminobutan-1-ol, 1-aminobutane-4-ol, N-methyl 1-aminobutane -4-ol, N-ethyl-1-aminobutan-4-ol, 1-amino-2-methylpropan-2-ol, 2-amino-2-methylprop N-1-ol, 1-aminopentan-4-ol, 2-amino-4-methylpentan-1-ol, 2-aminohexane-1-ol, 3-aminoheptan-4-ol, 1-aminooctane -2-ol, 5-aminooctane-4-ol, 1-aminopropane-2,3-diol, 2-aminopropane-1,3-diol, tris (oxymethyl) aminomethane, 1,2-diaminopropane- Preferred are alkanolamines such as 3-ol, 1,3-diaminopropan-2-ol, 2- (2-aminoethoxy) ethanol, 2- (2-aminoethylamino) ethanol, diglycolamine, and the like. These can be used alone or in combination. Among these, 1-amino-2-propanol is particularly preferable. The amine compound is preferably contained in an amount of 0.50 to 2.00% by mass, more preferably 1.00% to 1.90% by mass, based on the total amount of the etching solution.

<Hydrogen peroxide decomposition inhibitor>
In the etching solution according to the present invention, hydrogen peroxide is used as an oxidizing agent. Since hydrogen peroxide self-decomposes, a decomposition inhibitor that suppresses the decomposition is added. This is for extending the life of the etching solution. Main hydrogen peroxide decomposition inhibitors include urea urea hydrogen peroxide stabilizers such as phenylurea, allylurea, 1,3-dimethylurea, thiourea, phenylacetamide, phenylethylene glycol, 1-propanol, Preferable examples include lower alcohols such as 2-propanol.

  Of these, phenylurea is preferable, and phenylurea and 1-propanol are more preferably used in combination. In the case of phenylurea, the hydrogen peroxide decomposition inhibitor is preferably contained in an amount of 0.05% to 0.20% by mass, more preferably 0.07% to 0.12% by mass with respect to the total amount of the etching solution. % Is good. In the case of a lower alcohol, it is preferably contained in an amount of 0.10% to 2.00% by mass, more preferably 0.80% to 1.20% by mass.

  These substances are considered to suppress the decomposition of hydrogen peroxide by acting on hydrogen peroxide and suppressing the generation of radicals. If phenylurea is contained in an amount exceeding 0.20% by mass with respect to the total amount of the etching solution, the phenyl group and hydrogen peroxide react to produce a precipitate different from the reaction product of the azole compound and hydrogen peroxide.

<Chelating agent>
As Cu and Mo are etched and dissolved in the etching solution, decomposition of hydrogen peroxide is promoted. The chelating agent is considered to suppress decomposition of hydrogen peroxide by coordinating to metal ions such as Cu and Mo and preventing the metal ions from coming into contact with hydrogen peroxide. Therefore, in this specification, the chelating agent may be considered as a hydrogen peroxide decomposition inhibitor.

  As the chelating agent, an aluminocarboxylic acid-based chelating agent such as ethylenediaminetetraacetic acid (EDTA), hydroxyethyliminodiacetic acid (HIDA), ethylenediamine-N, N′-disuccinic acid (EDDS) is preferably used. The chelating agent is preferably contained in an amount of 0.50 mass% to 1.00 mass%, more preferably 0.60 mass% to 0.90 mass%, based on the total amount of the etching solution.

<Polyether>
The polyether can be an inhibitor of Cu etching rate. When polyether is used, the taper angle of the etching cross section becomes small, so that it can be suitably used for adjusting the taper angle. In particular, when there is sulfuric acid as an inorganic acid, the effect is great. As the polyether, polyethylene glycol (PEG) can be preferably used. Polyethylene glycol is preferably contained in an amount of 0.10% by mass to 0.50% by mass, more preferably 0.20% by mass to 0.40% by mass with respect to the total amount of the etching solution.

<Copper ion>
It has been confirmed that the etching rate according to the present invention changes as the Cu ion concentration increases as etching progresses and Cu ions and Mo ions are included. The operation of the etching equipment is controlled by adding an etching concentrate and hydrogen peroxide so that the change in etching rate is within a certain allowable range. Is preferred. Therefore, the etching solution may contain a predetermined range of Cu ions. Specifically, if the Cu ions are contained in an amount of 500 ppm to 7000 mmp, preferably 2000 ppm to 4000 ppm with respect to the total amount of the etching solution, a change in the etching rate can be easily assumed.

<Others>
In addition to these components, various commonly used additives may be added to the etching solution of the present invention as long as water and etching performance are not impaired. Since water is used for precision processing, it is preferable that water does not exist. Pure water or ultrapure water is preferable.

<PH, temperature>
The etching solution according to the present invention is preferably used in the range of pH 2 to 5, more preferably pH 3 to 4.5. The etching solution according to the present invention can be used between 18 ° C. and 40 ° C. More preferably, it is 18 degreeC to 35 degreeC, Most preferably, 20 degreeC to 32 degreeC is good.

<Save>
Hydrogen peroxide is used for the etching solution according to the present invention. Hydrogen peroxide is self-degrading. Therefore, the etchant contains a hydrogen peroxide decomposition inhibitor. However, when storing, the hydrogen peroxide solution and other liquids may be stored separately. Alternatively, a raw material excluding hydrogen peroxide and copper ions (referred to as an “etching liquid raw material”) and water may be mixed to prepare an etching liquid raw material solution. This solution may be water in a proportion smaller than the proportion of water in the etching solution shown in the examples described later.

  A solution of the etchant raw material prepared by mixing the etchant raw material and water is called an “etching concentrate”. The etching concentrate has a smaller volume as compared with the etching liquid because there is no hydrogen peroxide, so it is convenient for storage and transport. Further, in order to further reduce the volume during storage and transfer, an “etching highly concentrated solution” in which water of the “etching concentrated solution” is reduced may be used. The highly concentrated etching solution contains 20% to 70% water. The etching concentrate contains more than 70% water. Therefore, the etching solution of the present invention may be completed by combining the etching concentrate and hydrogen peroxide solution, or may be completed by combining the etching high concentration solution, water, and hydrogen peroxide solution.

<Etching method>
The target for using the etching solution according to the present invention is a multilayer film of copper layer / molybdenum layer in which molybdenum is a lower layer and copper is an upper layer. The lower molybdenum layer is thinner than the upper 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. If the range of t0 / t1 is out of this range and the Mo layer is too thick, the Mo layer residue tends to be generated, and conversely, if it is too thin, the Cu layer can no longer serve as an underlayer.

  The substrate and the base layer on which the molybdenum layer and the copper layer are formed are not particularly limited, and include glass, silicon, amorphous silicon, IGZO (Indium, Gallium, Zinc), oxygen ( It may be a metal oxide such as an amorphous semiconductor composed of Oxide).

  The etching solution according to the present invention can be stored by storing the hydrogen peroxide solution, the highly concentrated etching solution, and water (hydrogen peroxide solution and the etching concentrated solution) separately during storage. Become. Therefore, in actual use, these are mixed to complete the etching solution. The blending method is not limited as long as the concentration of hydrogen peroxide finally reaches a predetermined concentration.

  As an example, an etching concentrated liquid in which an etching liquid raw material is mixed in a certain amount of water is prepared. Hydrogen peroxide is usually supplied as a hydrogen peroxide solution having a concentration higher than that of the etching solution according to the present invention. Therefore, a predetermined amount of hydrogen peroxide solution and etching concentrate is prepared. This step may be called a step of preparing a multilayer film etching solution. Alternatively, an etching solution may be prepared by preparing a high etching concentration solution, water, and hydrogen peroxide solution having a higher concentration than the etching concentration solution.

  Copper ions can be mixed at any stage of preparing an etching concentrate (or highly concentrated etching solution) with an etchant raw material and water, or when preparing an etching solution with an etching concentrate and hydrogen peroxide. it can. Of course, the etching solution may be added after being prepared. In addition, when an etching concentrate and hydrogen peroxide water are additionally added to the etching solution already used, it is not necessary to add copper ions. This is because copper ions are already present in the etching solution.

  When performing the etching, as described above, the etching solution is used under the conditions of pH 2 to 5 and 18 ° C. to 40 ° C. Therefore, it is desirable that the object to be etched is also preheated to this temperature. The method for bringing the substrate to be treated into contact with the etching solution is not particularly limited. An etching solution may be sprayed on the substrate to be processed from above as in a shower type, or a method of dipping the substrate to be processed into a pool of etching solution may be used. This step may be called a step of bringing the multilayer film etching solution into contact with the substrate to be processed.

  In addition, the substrate to be processed is formed by laminating a molybdenum layer (Mo layer) and a copper layer (Cu layer) on a base material such as glass, and a pattern of a resist layer for pattern formation is formed on the laminated film. It is a substrate in a state of being.

<Description of various evaluation methods>
For the etching solution according to the present invention, the etching rate of copper and molybdenum (nm / min), the taper angle (°) of the cross section of the etched wiring, the undercut of the molybdenum layer, the molybdenum layer remaining on the substrate ( Evaluation was performed on the items of “Mo residue”), over-etching resistance, presence of precipitates, and hydrogen peroxide decomposition rate (mass% / day).

  The etching rate was measured as follows. First, a single layer film having a thickness of 300 nm for copper and 150 nm for molybdenum was formed on a silicon wafer on which a thermal oxide film of 100 nm was formed by sputtering. The copper film and the molybdenum film were brought into contact with an etching solution at 30 ° C. (may be 35 ° C. in some comparative examples) for 20 to 60 seconds.

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

  The taper angle was measured as follows. First, a molybdenum layer having a thickness of 20 nm was formed on a glass substrate by a sputtering method, and a copper layer having a thickness of 300 nm was subsequently formed thereon to prepare a Cu / Mo multilayer film sample. A resist patterned into a wiring shape was formed on the copper layer, and a substrate for taper angle evaluation was obtained. That is, the taper angle evaluation base material includes a substrate, a molybdenum layer, a copper layer thereon, and a patterned resist layer on the copper layer. Etching was performed by immersing this base for taper angle evaluation in an etching solution for the time of just etching. After the etching sample was washed and dried, the wiring portion was cut and the cut surface was observed.

  Observation of the cut surface was performed using SEM (Scanning Electron Microscope) (Hitachi: SU8020 type) under the conditions of an acceleration voltage of 1 kV and 30,000 to 50,000 times. Note that just etching is the time from the start of etching until the film transmits light. The time when the film transmitted light was visually confirmed.

  The cut surface shape is shown in FIG. As shown in FIG. 1A, an angle 5 formed by the substrate 1 and the etched inclined surface 6 is a taper angle (°). If the taper angle was 30 to 60 °, it was judged as a circle (◯). If it was out of the range of this angle, it was judged as X (x). “Mal” means success or success, and “X” means failure or failure. The same applies to the following evaluations. In FIG. 1A, the Mo layer is indicated by reference numeral 3, the Cu layer is indicated by reference numeral 2, and the resist layer is indicated by reference numeral 4.

  The undercut of the molybdenum layer means a state (reverse taper) in which the space between the molybdenum layer 3 and the substrate 1 is etched earlier than the copper layer, as indicated by reference numeral 10 in FIG. The evaluation can be performed simultaneously with the evaluation of the taper angle. If the undercut of the molybdenum layer was not found by observation at 30,000 to 50,000 times that of the SEM, it was judged as a circle (○), and if found, it was judged as a cross (×).

  The Mo residue was determined to be cross (X) when the residue was confirmed by observation with an optical microscope and SEM, and was determined to be round (◯) when the residue was not confirmed. The optical microscope was observed with bright field observation and dark field observation at a magnification of about 100 times. In SEM, observation was performed at 30,000 to 50,000 times.

  Overetching resistance (also referred to as “OE resistance”) refers to the taper angle, undercut of the molybdenum layer, and Mo residue when etching is performed twice as long as the time required for just etching. "In the case of evaluation, it was judged as Maru (○). If any one of them is judged as “X”, it is X (X).

  Presence / absence of precipitates was determined by visually determining whether or not precipitates were formed in the bottle after the etching solution was prepared and allowed to stand at room temperature for a predetermined time (several days) in a bottle. In the case where precipitates are generated, the etching solution is filtered with a filter paper, the foreign matter remaining on the filter paper is washed with pure water and dried at room temperature, and the obtained crystals and powders are converted into FT-IR (Shimadzu IR affinity). ) And SEM-EDX (manufactured by Horiba Seisakusho). If the precipitate was not visually observed, it was judged as round (◯), and if it was visually confirmed, it was judged as X (x).

  In the etching solution, it is important that precipitates are not generated and that the cross-sectional shape of the wiring is appropriate, but the decomposition rate of hydrogen peroxide is also an important item in order to lengthen the bath life. For reference, the hydrogen peroxide decomposition rate was also examined as an evaluation item.

  Decomposition rate of hydrogen peroxide is measured immediately after the preparation of the etching solution and after the elapse of a predetermined time (about 24 hours), with a titration reagent of potassium permanganate, and an automatic titrator (GP-200 manufactured by Mitsubishi Chemical Analytech). And measured. Then, the decomposition rate was calculated from the amount of change in the hydrogen peroxide concentration.

  If the amount of decrease in the hydrogen peroxide concentration after 24 hours (day) was less than 1.0% by mass, a circle (◯) evaluation was made, and if it was 1.0% by mass or more, a cross (x) evaluation was made. In addition, even if the hydrogen peroxide decomposition rate is X, if the other items are round, it may be referred to as the etching solution according to the present invention. In addition, regarding all the evaluations, although the conditions for the round evaluation were not satisfied, a value extremely close to the boundary value was evaluated as a triangle (Δ).

Example 1
0.06% by mass of sulfuric acid,
2.50% by mass of glycolic acid,
0.44% by weight of aspartic acid,
0.87% by mass of glutamic acid,
0.66% by mass of β-alanine,
1.61% by mass of 1 amino 2-propanol,
0.11% by mass of phenylurea,
0.88% by mass of ethylenediaminetetraacetic acid (hereinafter also referred to as “EDTA”)
An etching liquid raw material consisting of 92.87% by mass of water was prepared to prepare an etching concentrated liquid.

  35% hydrogen peroxide and an etching concentrate were mixed to prepare an etching solution having a hydrogen peroxide concentration of 5.30% by mass. Further, copper sulfate was added to prepare a copper ion concentration of 2000 ppm. The liquid temperature was 30 ° C. Table 1 shows the concentration of each component in the entire etching solution and the result of each evaluation item.

(Example 2)
0.07% by mass of sulfuric acid,
2.50% by mass of glycolic acid,
0.45% by weight of aspartic acid,
0.88% by mass of glutamic acid,
0.66% by mass of β-alanine,
1.61% by mass of 1 amino 2-propanol,
0.11% by mass of phenylurea,
0.88% by mass of ethylenediaminetetraacetic acid
0.33% by mass of polyethylene glycol (hereinafter also referred to as “PEG”)
An etching solution raw material consisting of 92.51% by mass of water was prepared to prepare an etching concentrate.

  35% hydrogen peroxide and an etching concentrate were mixed to prepare an etching solution having a hydrogen peroxide concentration of 5.30% by mass. Further, copper sulfate was added to prepare a copper ion concentration of 2000 ppm. The liquid temperature was 30 ° C. Table 1 shows the concentration of each component in the entire etching solution and the result of each evaluation item.

(Example 3)
0.19 mass% nitric acid,
2.05% by mass of glycolic acid,
0.44% by weight of aspartic acid,
0.90% by mass of glutamic acid,
0.66% by mass of β-alanine,
1.94% by mass of 1 amino 2-propanol
0.11% by mass of phenylurea,
0.87% by mass of ethylenediaminetetraacetic acid
The etching liquid raw material which consists of was mixed with 92.84 mass% of water, and the etching concentrated liquid was prepared.

  35% hydrogen peroxide and an etching concentrate were mixed to prepare an etching solution having a hydrogen peroxide concentration of 5.30% by mass. Further, copper sulfate was added to prepare a copper ion concentration of 2000 ppm. The liquid temperature was 30 ° C. Table 1 shows the concentration of each component in the entire etching solution and the result of each evaluation item.

Example 4
0.18% by mass of nitric acid,
2.55% by mass of glycolic acid,
0.45% by weight of aspartic acid,
0.91% by mass of glutamic acid,
β-alanine 0.69% by mass,
1.66% by mass of 1 amino 2-propanol,
0.11% by mass of phenylurea,
1.20% by mass of 1-propanol
The etching liquid raw material consisting of was mixed with 92.5% by mass of water to prepare an etching concentrated liquid.

  35% hydrogen peroxide and an etching concentrate were mixed to prepare an etching solution having a hydrogen peroxide concentration of 5.30% by mass. Further, copper sulfate was added to prepare a copper ion concentration of 2000 ppm. The liquid temperature was 30 ° C. Table 1 shows the concentration of each component in the entire etching solution and the result of each evaluation item.

(Example 5)
0.05% by mass of sulfuric acid,
2.47% by mass of glycolic acid,
0.44% by weight of aspartic acid,
0.87% by mass of glutamic acid,
1.17% by mass of glycine,
1.61% by mass of 1 amino 2-propanol,
0.11% by mass of phenylurea,
0.87% by mass of ethylenediaminetetraacetic acid
An etching solution raw material consisting of 92.41% by mass of water was prepared to prepare an etching concentrate.

  35% hydrogen peroxide and an etching concentrate were mixed to prepare an etching solution having a hydrogen peroxide concentration of 5.30% by mass. Further, copper sulfate was added to prepare a copper ion concentration of 2000 ppm. The liquid temperature was 30 ° C. Table 1 shows the concentration of each component in the entire etching solution and the result of each evaluation item.

(Example 6)
0.07% by mass of sulfuric acid,
2.46% by mass of glycolic acid,
0.44% by weight of aspartic acid,
0.87% by mass of glutamic acid,
1.74% by mass of β-alanine,
1.58% by mass of 1 amino 2-propanol,
0.11% by mass of phenylurea,
The etching liquid raw material which consists of was mixed with 92.73 mass% of water, and the etching concentrated liquid was prepared.

  35% hydrogen peroxide and an etching concentrate were mixed to prepare an etching solution having a hydrogen peroxide concentration of 5.30% by mass. Further, copper sulfate was added to prepare a copper ion concentration of 2000 ppm. The liquid temperature was 30 ° C. Table 1 shows the concentration of each component in the entire etching solution and the result of each evaluation item.

(Example 7)
0.07% by mass of sulfuric acid,
2.50% by mass of glycolic acid,
0.61% by mass of citric acid,
1.58% by mass of 1 amino 2-propanol,
0.11% by mass of phenylurea,
An etching liquid raw material consisting of 95.13% by mass of water was prepared to prepare an etching concentrated liquid.

  35% hydrogen peroxide and an etching concentrate were mixed to prepare an etching solution having a hydrogen peroxide concentration of 5.30% by mass. Further, copper sulfate was added to prepare a copper ion concentration of 2000 ppm. The liquid temperature was 30 ° C. Table 1 shows the concentration of each component in the entire etching solution and the result of each evaluation item.

(Example 8)
0.07% by mass of sulfuric acid,
2.27% by mass of glycolic acid,
0.66% by mass of β-alanine,
1.94% by mass of 1 amino 2-propanol
0.11% by mass of phenylurea,
0.87% by mass of ethylenediaminetetraacetic acid
0.34% by mass of polyether
An etching liquid raw material consisting of 93.74% by mass of water was prepared to prepare an etching concentrated liquid.

  35% hydrogen peroxide and an etching concentrate were mixed to prepare an etching solution having a hydrogen peroxide concentration of 5.30% by mass. Further, copper sulfate was added to prepare a copper ion concentration of 2000 ppm. The liquid temperature was 30 ° C. Table 1 shows the concentration of each component in the entire etching solution and the result of each evaluation item.

<Comparative example using azole compound>
(Comparative Example 1)
5.62% by mass of glycolic acid,
5.20% by mass of glycine,
1.31% by mass of 1 amino 2-propanol,
0.11% by mass of phenylurea,
0.13 mass% of 5-amino 1H tetrazole
The etching liquid raw material which consists of was mix | blended with 87.63 mass% of water, and prepared the etching concentrated liquid.

  35% hydrogen peroxide and an etching concentrate were mixed to prepare an etching solution having a hydrogen peroxide concentration of 5.30% by mass. Further, copper sulfate was added to prepare a copper ion concentration of 2000 ppm. The liquid temperature was 35 ° C. Table 2 shows the concentration of each component in the entire etching solution and the result of each evaluation item.

(Comparative Example 2)
3.91% by mass nitric acid,
4.33 mass% glycine,
3.86% by mass of 1 amino 2-propanol,
0.11% by mass of phenylurea,
0.11% by mass of 5-amino-1H tetrazole
An etching solution raw material consisting of 87.68% by mass of water was prepared to prepare an etching concentrate.

  35% hydrogen peroxide and an etching concentrate were mixed to prepare an etching solution having a hydrogen peroxide concentration of 5.30% by mass. Further, copper sulfate was added to prepare a copper ion concentration of 2000 ppm. The liquid temperature was 35 ° C. Table 2 shows the concentration of each component in the entire etching solution and the result of each evaluation item.

(Comparative Example 3)
2.42% by mass of glycolic acid,
1.25% by mass of glycine,
0.67% by mass of 1 amino 2-propanol,
0.12% by mass of phenylurea,
0.09 mass% of 5-amino 1H tetrazole
The etching liquid raw material consisting of was mixed with 95.45% by mass of water to prepare an etching concentrated liquid.

  35% hydrogen peroxide and an etching concentrate were mixed to prepare an etching solution having a hydrogen peroxide concentration of 5.30% by mass. Further, copper sulfate was added to prepare a copper ion concentration of 2000 ppm. The liquid temperature was 35 ° C. Table 2 shows the concentration of each component in the entire etching solution and the result of each evaluation item.

(Comparative Example 4)
2.65% by mass of glycolic acid,
1.00% by mass of glycine,
β-alanine 0.82% by mass,
0.39 mass% of 1 amino 2-propanol,
0.12% by mass of phenylurea,
0.12 mass% of 5-amino 1H tetrazole
An etching liquid raw material consisting of 94.90% by mass of water was prepared to prepare an etching concentrated liquid.

  35% hydrogen peroxide and an etching concentrate were mixed to prepare an etching solution having a hydrogen peroxide concentration of 5.30% by mass. Further, copper sulfate was added to prepare a copper ion concentration of 2000 ppm. The liquid temperature was 35 ° C. Table 2 shows the concentration of each component in the entire etching solution and the result of each evaluation item.

(Comparative Example 5)
0.12% by mass of nitric acid,
2.45% by mass of guanic acid,
2.62% by mass of 1 amino 2-propanol,
0.08% by mass of phenylurea,
0.29 mass% of 5-amino 1H tetrazole
An etching solution raw material consisting of 94.44% by mass of water was prepared to prepare an etching concentrate.

  35% hydrogen peroxide and an etching concentrate were mixed to prepare an etching solution having a hydrogen peroxide concentration of 5.30% by mass. Further, copper sulfate was added to prepare a copper ion concentration of 2000 ppm. The liquid temperature was 35 ° C. Table 2 shows the concentration of each component in the entire etching solution and the result of each evaluation item.

(Comparative Example 6)
0.08% by mass nitric acid,
2.20% by mass of glycolic acid,
3.98% by mass of malonic acid,
1.01% by mass of lactic acid,
1.64% by mass of 1 amino 2-propanol
0.12% by mass of phenylurea,
0.14 mass% of 5-amino 1H tetrazole
An etching solution raw material consisting of 89.83% by mass of water was prepared to prepare an etching concentrate.

35% hydrogen peroxide and an etching concentrate were mixed to prepare an etching solution having a hydrogen peroxide concentration of 5.30% by mass. Further, copper sulfate was added to prepare a copper ion concentration of 2000 ppm. The liquid temperature was 35 ° C. Table 2 shows the concentration of each component in the entire etching solution and the result of each evaluation item.
<Comparative example without azole compound>

(Comparative Example 7)
2.65% by mass of glycolic acid,
1.00% by mass of lactic acid,
2.52% by mass of 1 amino 2-propanol,
0.11% by mass of phenylurea,
The etching liquid raw material which consists of with 93.72 mass% of water was prepared, and the etching concentrated liquid was prepared.

  35% hydrogen peroxide and an etching concentrate were mixed to prepare an etching solution having a hydrogen peroxide concentration of 5.30% by mass. Further, copper sulfate was added to prepare a copper ion concentration of 2000 ppm. The liquid temperature was 35 ° C. Table 3 shows the concentration of each component in the entire etching solution and the result of each evaluation item.

(Comparative Example 8)
3.54% by mass of malonic acid,
1.40% by mass of glycine,
1.64% by mass of 1 amino 2-propanol,
0.11% by mass of phenylurea,
An etching solution raw material consisting of 93.31% by mass of water was prepared to prepare an etching concentrate.

  35% hydrogen peroxide and an etching concentrate were mixed to prepare an etching solution having a hydrogen peroxide concentration of 5.30% by mass. Further, copper sulfate was added to prepare a copper ion concentration of 2000 ppm. The liquid temperature was 35 ° C. Table 3 shows the concentration of each component in the entire etching solution and the result of each evaluation item.

(Comparative Example 9)
3.61% by mass of citric acid,
1.43% by mass of glycine,
1.64% by mass of 1 amino 2-propanol,
0.11% by mass of phenylurea,
The etching liquid raw material which consists of was mixed with water 93.21 mass%, and the etching concentrated liquid was prepared.

  35% hydrogen peroxide and an etching concentrate were mixed to prepare an etching solution having a hydrogen peroxide concentration of 5.30% by mass. Further, copper sulfate was added to prepare a copper ion concentration of 2000 ppm. The liquid temperature was 35 ° C. Table 3 shows the concentration of each component in the entire etching solution and the result of each evaluation item.

(Comparative Example 10)
4.73% by mass of lactic acid,
1.39% by mass of glycine,
1.72% by mass of 1 amino 2-propanol,
0.11% by mass of phenylurea,
The etching liquid raw material consisting of was mixed with 92.05% by mass of water to prepare an etching concentrated liquid.

  35% hydrogen peroxide and an etching concentrate were mixed to prepare an etching solution having a hydrogen peroxide concentration of 5.30% by mass. Further, copper sulfate was added to prepare a copper ion concentration of 2000 ppm. The liquid temperature was 35 ° C. Table 3 shows the concentration of each component in the entire etching solution and the result of each evaluation item.

(Comparative Example 11)
2.80% by mass of glycolic acid,
1.41% by mass of glycine,
1.25% by mass of 1 amino 2-propanol,
0.11% by mass of phenylurea,
The etching liquid raw material consisting of 94.43% by mass of water was prepared to prepare an etching concentrated liquid.

  35% hydrogen peroxide and an etching concentrate were mixed to prepare an etching solution having a hydrogen peroxide concentration of 5.30% by mass. Further, copper sulfate was added to prepare a copper ion concentration of 2000 ppm. The liquid temperature was 35 ° C. Table 3 shows the concentration of each component in the entire etching solution and the result of each evaluation item.

<Result>
Examples 1 to 8 are etching solutions according to the present invention. Since no azole compound is contained, no reaction product is formed with hydrogen peroxide, and there is no precipitation portion. Three types of acid, organic acid, glycolic acid, aspartic acid, and glutamic acid were used simultaneously. Among these, those using EDTA or 1 propanol (Examples 1 to 5) are free from precipitates and have a taper angle, Mo undercut, Mo residue, O.D. E. All items of resistance were rated as maru. Furthermore, the hydrogen peroxide decomposition rate was less than 0.1% by mass / day, and desirable results could be obtained.

  Further, since the over-etching resistance was good, it was possible to perform etching while maintaining a good taper angle from the time spent for just etching to twice the time. Moreover, even if the film thickness ratio (t0 / t1) of Mo and Cu differs from the case (20/300) of an Example, the etching ratio of these Examples is 0.01 to 0.2. In the range between 30 ° and 60 °, a taper angle of 30 ° to 60 ° could be realized.

  In Example 6, as compared with Example 5, the neutral organic acid was replaced from glycine to β-alanine, and EDTA was not added. When EDTA was removed, the decomposition rate (mass% / day) of hydrogen peroxide exceeded 1.0 mass% / day. However, the cross-sectional shape of the etched wiring was good.

  Examples 7 and 8 are examples in which the etching angle of Cu and Mo was adjusted using glycolic acid and citric acid or glycolic acid and β-alanine, and the taper angle could be formed within a suitable range. However, the hydrogen peroxide decomposition rate slightly exceeded 1.0 mass% / day. From these facts, it can be said that the etching solution according to the present invention contains at least glycolic acid as an organic acid, and has hydrogen peroxide, an inorganic acid, an amine compound, and a hydrogen peroxide stabilizer. A chelating agent may also be included.

  Comparative Examples 1 to 6 are examples in which an azole compound is included. As the azole compound, 5 amino 1H tetrazole was used. The effect of using the azole compound is that the etching rate of Mo can be increased while suppressing the etching rate of Cu. Therefore, the taper angle can be controlled by balancing with the inorganic acid.

  In Comparative Examples 1 to 5, the etching rate of Mo was large and the taper angle was large. Comparative Example 6 has a well-adjusted composition, and a mixture of glycolic acid, malonic acid, and lactic acid was used to increase only the copper etching rate. In Comparative Example 6, the taper angle obtained favorable results. However, the Mo etching rate was still high, and when overetching was performed, the Mo layer was slightly undercut.

  Comparative Examples 1 to 6 had compositions capable of adjusting the taper angle as described above, but the azole compound and hydrogen peroxide reacted to generate precipitates.

  Comparative Examples 7 to 11 are examples in which no azole compound is contained. As shown in Comparative Examples 1 to 6, the etching rate of Cu and Mo could be adjusted with a combination of an inorganic acid and an azole compound. Comparative Examples 7 to 11 are intended to adjust the etching rate of Cu and Mo by adjusting the organic acid and amine as the case where no azole compound is used. As the amine, 1 amino 2-propanol was used.

  In Comparative Example 7, glycolic acid and lactic acid were used as organic acids, but the taper angle was small. In Comparative Example 8, malonic acid and glycine were used, but the etching rate of Cu was too high and no film remained. In Comparative Examples 9 to 11, the types of the neutral organic acid and the acidic organic acid were changed, but the etching rate of Cu was high, and the taper angle was not able to obtain a good shape. However, since no azole compound was contained, no precipitate was generated.

  In the examples, as demonstrated in Comparative Examples 7 to 11, no azole compound is used, and thus no precipitate is generated. Moreover, compared with Comparative Examples 7 to 11, the ratio of the etching rate of Cu and Mo is adjusted by using glycolic acid, aspartic acid, and glutamic acid simultaneously, and using either EDTA or 1-propanol of lower alcohol. As a result, it was possible to realize an etching solution having a suitable cross-sectional shape of the etching portion and no precipitate and a long bath life.

  The etching solution of the present invention can be applied to a substrate such as a glass substrate, a silicon substrate, an amorphous silicon substrate, or a metal oxide substrate, or a base layer made of these materials, regardless of products such as liquid crystal displays, plasma displays, and organic EL FPDs. It can be widely used in a situation where a wiring in which a molybdenum layer and a copper layer formed on each other are used.

1 Substrate 2 Copper layer 3 Molybdenum layer 4 Resist (layer)
5 Taper angle 6 Slope 10 Undercut part

More specifically, an etching solution for a multilayer film including a copper layer and a molybdenum layer according to the present invention,
Hydrogen peroxide,
And at least any one of sulfuric acid or nitric acid with an inorganic acid,
Is an acidic organic acid, one or a plurality of types comprising at least glycolic acid glycolic acid, aspartic acid, glutamic acid, citric acid,
One and one of glycine and β-alanine as a neutral organic acid,
And 1-amino-2-propanol with an amine compound,
Look including phenyl urea or a lower alcohol as a hydrogen peroxide decomposition inhibitor,
The hydrogen peroxide is 3.50 mass% to 5.80 mass% of the total amount of the etching solution,
The inorganic acid is 0.01% by mass to 0.50% by mass with respect to the total amount of the etching solution,
The acidic organic acid is 1% by mass to 7% by mass with respect to the total amount of the etching solution,
The neutral organic acid is 0.10% by mass to 3.00% by mass with respect to the total amount of the etching solution,
The amine compound is 0.50% by mass to 2.00% by mass with respect to the total amount of the etching solution,
The hydrogen peroxide decomposition inhibitor is 0.05% by mass to 0.20% by mass with respect to the total amount of the etching solution.
PH as an etching solution is 2-5,
An azole compound, a phosphorus compound, and a fluorine compound are not included .

Moreover, the etching liquid which concerns on this invention can be comprised in the state of a concentrate so that it may not become bulky at the time of a preservation | save or a transfer. More specifically, an etching concentrate for a multilayer film comprising a copper layer and a molybdenum layer according to the present invention,
And at least any one of sulfuric acid or nitric acid with an inorganic acid,
Is an acidic organic acid, one or a plurality of types comprising at least glycolic acid glycolic acid, aspartic acid, glutamic acid, citric acid,
One and one of glycine and β-alanine as a neutral organic acid,
And 1-amino-2-propanol with an amine compound,
Look including phenyl urea or a lower alcohol and water as the hydrogen peroxide decomposition inhibitor,
The inorganic acid is 0.01% by mass to 0.50% by mass with respect to the total amount of the etching solution,
The acidic organic acid is 1% by mass to 7% by mass with respect to the total amount of the etching solution,
The neutral organic acid is 0.10% by mass to 3.00% by mass with respect to the total amount of the etching solution,
The amine compound is 0.50% by mass to 2.00% by mass with respect to the total amount of the etching solution,
The hydrogen peroxide decomposition inhibitor is 0.05% by mass to 0.20% by mass with respect to the total amount of the etching solution.
An azole compound, a phosphorus compound, and a fluorine compound are not included .

In addition, the etching method for multilayer film including the copper layer molybdenum layer according to the present invention,
And at least any one of sulfuric acid or nitric acid with an inorganic acid,
Is an acidic organic acid, one or a plurality of types comprising at least glycolic acid glycolic acid, aspartic acid, glutamic acid, citric acid,
One and one of glycine and β-alanine as a neutral organic acid,
And 1-amino-2-propanol with an amine compound,
Look including phenyl urea or a lower alcohol and water as the hydrogen peroxide decomposition inhibitor,
The inorganic acid is 0.01% by mass to 0.50% by mass with respect to the total amount of the etching solution,
The acidic organic acid is 1% by mass to 7% by mass with respect to the total amount of the etching solution,
The neutral organic acid is 0.10% by mass to 3.00% by mass with respect to the total amount of the etching solution,
The amine compound is 0.50% by mass to 2.00% by mass with respect to the total amount of the etching solution,
The hydrogen peroxide decomposition inhibitor is 0.05% by mass to 0.20% by mass with respect to the total amount of the etching solution.
An etching solution for a multilayer film is prepared by preparing an azole compound, a phosphorus compound, an etching concentrate containing no fluorine compound , water, and 3.50% by mass to 5.80% by mass of hydrogen peroxide based on the total amount of the etching solution. And a process of
Look including the step of contacting the multi-layer film for an etching solution on a substrate to be processed,
In the step of bringing the multilayer film etching solution into contact with the substrate to be processed,
The multilayer film etching solution has a pH in the range of 2 to 5 and a solution temperature of 18 ° C. to 35 ° C.

Claims (14)

Hydrogen peroxide,
Inorganic acids,
An acidic organic acid,
Neutral organic acids,
An amine compound;
A multilayer film etching solution comprising a copper layer and a molybdenum layer, characterized by comprising a hydrogen peroxide decomposition inhibitor.   The multilayer film etching solution containing a copper layer and a molybdenum layer according to claim 1, which does not contain an azole compound, a phosphorus compound, and a fluorine compound.   Furthermore, the aminocarboxylic acid type chelating agent is contained, The etching liquid for multilayer films containing the copper layer and molybdenum layer as described in any one of Claim 1 or 2 characterized by the above-mentioned. The said inorganic acid is at least one of a sulfuric acid or nitric acid, The etching liquid for multilayer films containing the copper layer and molybdenum layer described in any one of the Claims 1 thru | or 3 characterized by the above-mentioned. 5. The multilayer organic etching including a copper layer and a molybdenum layer according to claim 1, wherein the acidic organic acid includes three types of glycolic acid, aspartic acid, and glutamic acid. liquid. 6. The multilayer film etching solution comprising a copper layer and a molybdenum layer according to claim 1, wherein the neutral organic acid is one of glycine and β-alanine. . The said amine compound is 1 amino 2-propanol, The etching liquid for multilayer films containing the copper layer and molybdenum layer described in any one of Claims 1 thru | or 6 characterized by the above-mentioned. 8. The multilayer film etching solution comprising a copper layer and a molybdenum layer according to claim 1, wherein the hydrogen peroxide decomposition inhibitor is phenylurea or lower alcohol. 9. The method according to claim 1, wherein the aluminocarboxylic acid-based chelating agent is any one of ethylenediaminetetraacetic acid, hydroxyethyliminodiacetic acid, and ethylenediamine-N, N′-disuccinic acid. Etching solution for multilayer film comprising copper layer and molybdenum layer described in 1. Furthermore, the etching liquid for multilayer films containing the copper layer and the molybdenum layer described in any one of Claims 1 thru | or 9 characterized by including polyethyleneglycol. Furthermore, 500-7000 ppm of copper ions are contained, The etching solution for multilayer films containing the copper layer and molybdenum layer described in any one of Claims 1 thru | or 10 characterized by the above-mentioned. Inorganic acids,
An acidic organic acid,
Neutral organic acids,
An amine compound;
A hydrogen peroxide decomposition inhibitor;
Etching concentrate for multilayer film containing copper layer and molybdenum layer, characterized by containing water. Inorganic acids,
An acidic organic acid,
Neutral organic acids,
An amine compound;
A step of preparing an etching solution for multilayer film by preparing an etching concentrate containing hydrogen peroxide decomposition inhibitor and water, water and hydrogen peroxide;
A method for etching a multilayer film including a copper layer and a molybdenum layer, comprising a step of bringing the multilayer film etching solution into contact with a substrate to be processed. In the step of bringing the multilayer film etching solution into contact with the substrate to be processed,
14. The multilayer including a copper layer and a molybdenum layer according to claim 13, wherein the multilayer etchant has a pH of 2 to 5 and a temperature of 18 ° C. to 35 ° C. 14. Method for etching the film.

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