Etching solution and etching method for copper-molybdenum film layer

Abstract

The invention relates to an etching solution and an etching method for a copper-molybdenum film layer, in particular to the field of semiconductor processing, and the etching solution for the copper-molybdenum film layer comprises an etching main agent; the etching main agent is prepared from the following raw materials in parts by weight: 9 to 11 parts of oxidizing agent, 5 to 8 parts of first organic acid chelating agent, 1 to 3 parts of first inorganic acid, 6 to 10 parts of first organic alkali, 0.5 to 2 parts of first ether alcohol, 0.01 to 0.05 part of first corrosion inhibitor, 0.01 to 0.05 part of purine compound and 70 to 80 parts of water; wherein the first organic acid chelating agent comprises phenolsulfonic acid. According to the etching solution provided by the invention, the components of the etching solution are reasonably designed, specific phenolsulfonic acid is introduced to regulate and control the etching solution, and meanwhile, by virtue of the synergistic effect of all the components, a good etching effect can be achieved when copper-molybdenum film layers with different thicknesses are etched.

Description

Technical Field

[0001] The present invention relates to the field of semiconductor processing, and particularly to an etching solution and an etching method for a copper-molybdenum film layer. Background Art

[0002] At present, the copper-molybdenum film layer is an important component structure applied in liquid crystal display devices. The copper material has a low resistivity, and the molybdenum material has good adhesion to substrates such as glass. Therefore, the quality of the copper-molybdenum film layer greatly affects the quality of liquid crystal display devices.

[0003] With the development of displays, high-contrast displays have received increasing attention. When the angle of the etching taper angle (Taper angle) of the gate electrode in the array substrate is reduced to a certain extent, the tail section of the gate electrode is longer, thereby blocking more light and enhancing the contrast between light and dark, which can significantly improve the contrast of the display. A copper-molybdenum etching solution with good performance has a good effect on etching the copper-molybdenum film layer, can form a good etching morphology, and reduce the generation of chamfers.

[0004] For example, CN112522705A discloses an etching agent for a copper-molybdenum film layer and an etching method for the copper-molybdenum film layer. The etching agent includes an etching main agent, and the etching main agent includes hydrogen peroxide, a chelating agent, a first inorganic acid, and water. The mass percentage content of the chelating agent in the etching main agent is 2%-10%, the mass percentage content of the first inorganic acid in the etching main agent is 1%-10%, and the mass percentage content of the hydrogen peroxide in the etching main agent is 4%-10%. By adjusting the ratio of the chelating agent to the inorganic acid, a smaller etching taper angle can be obtained to meet the requirements of higher contrast of the display panel. At the same time, there will be no phenomena such as film undercut or molybdenum residue that are likely to cause defects in the display panel.

[0005] However, in the actual use process, it is found that when etching copper-molybdenum film layers with different thickness ratios (such as ), under the same CD-Loss requirement, since Mo metal is relatively difficult to etch and the thickness is different, when the CD-Loss is the same, there may be residues in the thicker Mo layer. At the same time, the etching rate of the molybdenum alloy will inevitably increase, which is extremely likely to cause chamfers in the thinner alloy, resulting in a low yield of the product. Summary of the Invention

[0006] In view of the problems existing in the prior art, the purpose of the present invention is to provide an etching solution and an etching method for a copper-molybdenum film layer to solve the defect that the currently used etching solution cannot be applied simultaneously when etching copper-molybdenum film layers with different thickness ratios, and the defects of poor chamfering effect and high residue obtained.

[0007] To achieve this purpose, the present invention adopts the following technical solutions:

[0008] In a first aspect, the present invention provides an etching solution for a copper-molybdenum film layer. The etching solution for the copper-molybdenum film layer includes: an etching main agent;

[0009] The raw materials of the etching main agent include, by weight:

[0010] 9-11 parts of an oxidizing agent, 5-8 parts of a first organic acid chelating agent, 1-3 parts of a first inorganic acid, 6-10 parts of a first organic base, 0.5-1 part of a first inorganic base, 0.5-2 parts of a first ether alcohol, 0.01-0.05 part of a first corrosion inhibitor, 0.01-0.05 part of a purine compound, and 70-80 parts of water;

[0011] Among them, the first organic acid chelating agent includes phenolsulfonic acid.

[0012] The etching solution provided by the present invention, through reasonable design of the components of the etching solution, introduces specific phenolsulfonic acid to regulate the etching solution, and at the same time, with the synergistic effect of each component, achieves good etching effects when etching copper-molybdenum film layers of different thicknesses, and has a good etching taper angle (Taper angle). For example, when etching, CD = 0.5μm, without residue, and can also meet the requirements when etching, CD = 1.30μm, without undercutting.

[0013] As a preferred technical solution of the present invention, the oxidizing agent includes: hydrogen peroxide and / or persulfate.

[0014] Preferably, the first organic acid chelating agent further includes: one or at least two combinations of malonic acid, malic acid, citric acid or acetic acid.

[0015] Preferably, the first organic acid chelating agent includes: acetic acid, malonic acid, malic acid and phenolsulfonic acid.

[0016] As a preferred technical solution of the present invention, the first inorganic acid includes: one or at least two combinations of nitric acid, sulfuric acid or phosphoric acid.

[0017] Preferably, the first organic base includes: one or at least two combinations of triethanolamine, isopropanolamine or triisopropanolamine.

[0018] Preferably, the first inorganic base includes: ammonia water with a mass concentration ≤ 10%.

[0019] As a preferred technical solution of the present invention, the first ether alcohol includes: one or at least two combinations of diethylene glycol monobutyl ether, ethylene glycol monobutyl ether or glycerol monomethyl ether.

[0020] ​Preferably, the first corrosion inhibitor includes one or a combination of at least two of: methylazole corrosion inhibitors, aminoazole corrosion inhibitors, and pyridine-3-carboxylic acid.

[0021] Preferably, the purine compound includes one or a combination of at least two of: purine, adenine, 2-aminopurine guanine, 7-deazaguanine, or hypoxanthine.

[0022] As a preferred technical solution of the present invention, the etchant for the copper-molybdenum film layer further includes: an etching adjuvant.

[0023] The raw materials of the etching adjuvant include, by weight:

[0024] 20-40 parts of a second organic acid chelating agent, 1-5 parts of a second inorganic acid, 10-20 parts of a second organic base, 1-2 parts of a second inorganic base, 1-3 parts of a second ether alcohol, 1-2 parts of a second corrosion inhibitor, and 40-50 parts of water.

[0025] As a preferred technical solution of the present invention, the second organic acid chelating agent includes a combination of at least 3 of: citric acid, malonic acid, acetic acid, or phenolsulfonic acid.

[0026] Preferably, the second organic acid chelating agent includes one of: a combination of citric acid, malonic acid, and acetic acid in a mass ratio of (3-5):1:1, a combination of malonic acid, acetic acid, and phenolsulfonic acid in a mass ratio of (1.5-3):1:1, a combination of citric acid, malonic acid, and phenolsulfonic acid in a mass ratio of (9-11):3:1, a combination of citric acid, acetic acid, and phenolsulfonic acid in a mass ratio of (3.5-4.5):2:1, or a combination of citric acid, malonic acid, acetic acid, and phenolsulfonic acid in a mass ratio of (3-5):2:1:1.

[0027] Preferably, the second inorganic acid includes one or a combination of at least two of: nitric acid, sulfuric acid, or phosphoric acid.

[0028] Preferably, the second organic base includes one or a combination of at least two of: triethanolamine, isopropanolamine, or triisopropanolamine.

[0029] Preferably, the second inorganic base includes ammonia water with a mass concentration ≤ 10%.

[0030] As a preferred technical solution of the present invention, the second ether alcohol includes one or a combination of at least two of: diethylene glycol butyl ether, ethylene glycol butyl ether, or glycerol monomethyl ether.

[0031] Preferably, the second corrosion inhibitor includes one or a combination of at least two of: methylazole corrosion inhibitors, aminoazole corrosion inhibitors, and pyridine-3-carboxylic acid.

[0032] Second aspect, the present invention provides an etching method for a copper molybdenum film layer, and the etching method includes: etching the copper molybdenum film layer with the etching solution as described in the first aspect.

[0033] As a preferred technical solution of the present invention, the etching method includes:

[0034] etching the copper molybdenum film layer with the main etching agent;

[0035] wherein, for every 1000 ppm increase in copper ions in the liquid phase during etching, an etching adjuvant accounting for 1-1.2% of the mass of the main etching agent is added.

[0036] As a preferred technical solution of the present invention, the temperature of the etching is 25-40 °C.

[0037] Compared with the prior art solutions, the present invention has the following beneficial effects:

[0038] (1) The two-component etching solution provided by the present invention has a moderate oxidant concentration, the etching solution life can reach 10,000 ppm, there is no crystallization and water residue, and after etching the copper molybdenum film, the lower limit of metal residue CD < 0.65 μm. After etching the copper molybdenum film, the lower limit of metal residue CD < 0.65 μm.

[0039] (2) The etching solution provided by the present invention is compatible with copper molybdenum film and copper molybdenum film two products. After etching, the large OE% has no chamfer and good morphology, that is, it can meet CD = 0.5 μm without residue, and can also meet the problem of no reverse chamfer for CD = 1.30 μm. The CD variation is small (≤0.1 μm), and the Taper variation is small (≤5°).

[0040] (3) The etching solution provided by the present invention has a fast etching time (<150 s), does not affect production capacity, realizes maximum output. At the same time, due to the excellent hydrophilicity of the etching solution, the water washing time can be shortened by 50%, and there is no foreign matter residue on the substrate, which not only greatly reduces the water washing consumption, but also can reduce the defective rate. BRIEF DESCRIPTION OF THE DRAWINGS

[0041] Figure 1 is the SEM photograph of the product obtained after etching the copper molybdenum film layer in Embodiment 1 of the present invention. of the copper molybdenum film layer after etching.

[0042] The present invention will be further described in detail below. However, the following examples are only simple examples of the present invention, and do not represent or limit the scope of the protection of the present invention. The scope of protection of the present invention is subject to the claims. DETAILED DESCRIPTION OF THE INVENTION

[0043] To better illustrate the present invention and facilitate understanding of its technical solution, typical but non-limiting embodiments of the present invention are as follows:

[0044] Currently, when preparing a copper molybdenum film layer, copper molybdenum film layers of different thicknesses are usually prepared to meet different requirements. For example a copper molybdenum film layer of a copper molybdenum film layer of. In devices used in displays, the copper molybdenum film layer often needs to be etched to form an etched tapered angle to ensure the contrast of the display. However, when the same etching solution etches copper molybdenum film layers with different thickness ratios and meets the requirement of the same molybdenum element residue rate, such as CD < 0.6 μm, when the etching of a copper molybdenum film layer can meet the requirements, the same etching solution will cause over-etching when etching a copper molybdenum film layer, resulting in chamfering, that is, the occurrence of the inverse Taper situation.

[0045] Based on the above problems, this embodiment provides an etching solution for a copper molybdenum film layer. The etching solution for the copper molybdenum film layer includes: an etching main agent;

[0046] The raw materials of the etching main agent include, by weight:

[0047] 9 - 11 parts of an oxidizing agent, 5 - 8 parts of a first organic acid chelating agent, 1 - 3 parts of a first inorganic acid, 6 - 10 parts of a first organic base, 0.5 - 1 part of a first inorganic base, 0.5 - 2 parts of a first ether alcohol, 0.01 - 0.05 part of a first corrosion inhibitor, 0.01 - 0.05 part of a purine compound, and 70 - 80 parts of water.

[0048] The etching main agent provided by the present invention can obtain excellent chamfering and remaining space when etching copper molybdenum film layers with different thickness ratios by virtue of the synergistic cooperation effect of organic acids, inorganic acids, and organic bases, which is beneficial to the efficient preparation of display panels.

[0049] In the present invention, for the raw materials of the etching main agent, the oxidizing agent is 9 - 11 parts by weight. For example, it can be 9 parts, 9.2 parts, 9.4 parts, 9.6 parts, 9.8 parts, 10 parts, 10.2 parts, 10.4 parts, 10.6 parts, 10.8 parts, or 11 parts, etc., but is not limited to the listed values. Other unlisted values within this range also meet the requirements.

[0050] In the present invention, for the raw materials of the etching main agent, the first organic acid chelating agent is 5 - 8 parts by weight. For example, it can be 5 parts, 5.2 parts, 5.4 parts, 5.6 parts, 5.8 parts, 6 parts, 6.2 parts, 6.4 parts, 6.6 parts, 6.8 parts, 7 parts, 7.2 parts, 7.4 parts, 7.6 parts, 7.8 parts, or 8 parts, etc., but is not limited to the listed values. Other unlisted values within this range also meet the requirements.

[0051] In the present invention, for the raw materials of the main etching agent, the first inorganic acid is 1-3 parts by weight. For example, it can be 1 part, 1.2 parts, 1.4 parts, 1.6 parts, 1.8 parts, 2 parts, 2.2 parts, 2.4 parts, 2.6 parts, 2.8 parts or 3 parts, etc., but not limited to the listed values. Other unlisted values within this range also meet the requirements.

[0052] In the present invention, for the raw materials of the main etching agent, the first organic base is 6-10 parts by weight. For example, it can be 6 parts, 6.2 parts, 6.4 parts, 6.6 parts, 6.8 parts, 7 parts, 7.2 parts, 7.4 parts, 7.6 parts, 7.8 parts, 8 parts, 8.2 parts, 8.4 parts, 8.6 parts, 8.8 parts, 9 parts, 9.2 parts, 9.4 parts, 9.6 parts, 9.8 parts or 10 parts, etc., but not limited to the listed values. Other unlisted values within this range also meet the requirements.

[0053] In the present invention, for the raw materials of the main etching agent, the first inorganic base is 0.5-1 part by weight. For example, it can be 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part or 1 part, etc., but not limited to the listed values. Other unlisted values within this range also meet the requirements.

[0054] In the present invention, for the raw materials of the main etching agent, the first ether alcohol is 0.5-2 parts by weight. For example, it can be 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part, 1 part, 1.1 part, 1.2 part, 1.3 part, 1.4 part, 1.5 part, 1.6 part, 1.7 part, 1.8 part, 1.9 part or 2 parts, etc., but not limited to the listed values. Other unlisted values within this range also meet the requirements.

[0055] In the present invention, for the raw materials of the main etching agent, the first corrosion inhibitor is 0.01-0.05 part by weight. For example, it can be 0.01 part, 0.015 part, 0.02 part, 0.025 part, 0.03 part, 0.035 part, 0.04 part, 0.045 part or 0.05 part, etc., but not limited to the listed values. Other unlisted values within this range also meet the requirements.

[0056] In the present invention, for the raw materials of the main etching agent, the purine compound is 0.01-0.05 part by weight. For example, it can be 0.01 part, 0.015 part, 0.02 part, 0.025 part, 0.03 part, 0.035 part, 0.04 part, 0.045 part or 0.05 part, etc., but not limited to the listed values. Other unlisted values within this range also meet the requirements.

[0057] In the present invention, for the raw materials of the main etching agent, water is 70 - 80 parts by weight, for example, it can be 70 parts, 71 parts, 72 parts, 73 parts, 74 parts, 75 parts, 76 parts, 77 parts, 78 parts, 79 parts or 80 parts, etc., but not limited to the listed values, and other unlisted values within this range also meet the requirements.

[0058] Among them, the oxidant includes: hydrogen peroxide and / or persulfate.

[0059] In the present invention, the mass concentration of the hydrogen peroxide used is 25 - 31%, for example, it can be 25%, 25.5%, 26%, 26.5%, 27%, 27.5%, 28%, 28.5%, 29%, 29.5%, 30%, 30.5% or 31%, etc., but not limited to the listed values, and other unlisted values within this range also meet the requirements.

[0060] Exemplarily, the persulfate used includes: sodium persulfate, potassium persulfate, ammonium persulfate, etc.

[0061] Among them, the first organic acid chelating agent includes phenol sulfonic acid.

[0062] In the present invention, the phenol sulfonic acid used includes: one or a combination of at least two of o - hydroxybenzenesulfonic acid, m - hydroxybenzenesulfonic acid or p - hydroxybenzenesulfonic acid.

[0063] In the present invention, the combinations of the phenol sulfonic acid used include: the combination of o - hydroxybenzenesulfonic acid and m - hydroxybenzenesulfonic acid, the combination of m - hydroxybenzenesulfonic acid and p - hydroxybenzenesulfonic acid, etc., the combination of o - hydroxybenzenesulfonic acid and p - hydroxybenzenesulfonic acid, the combination of o - hydroxybenzenesulfonic acid, m - hydroxybenzenesulfonic acid and p - hydroxybenzenesulfonic acid, etc.

[0064] Among them, the first organic acid chelating agent further includes: one or a combination of at least two of malonic acid, malic acid, citric acid or acetic acid. Preferably, the first organic acid chelating agent includes: acetic acid, malonic acid, malic acid and phenol sulfonic acid with a mass ratio of 1:(1.8 - 2.2):1:(1.7 - 2.5).

[0065] Exemplarily, for the combinations of malonic acid, malic acid, citric acid or acetic acid used, it can be selected as the combination of malonic acid and malic acid with a mass ratio of (1.8 - 2.2):1, the combination of malic acid and citric acid with a mass ratio of 1:(2.8 - 3.5), the combination of citric acid and acetic acid with a mass ratio of (1.8 - 2.2):1, the combination of malonic acid and acetic acid with a mass ratio of (1.8 - 2.2):1, etc.

[0066] In the present invention, by preferably using the combination reagent of acetic acid, malonic acid, malic acid and phenol sulfonic acid as the first organic acid chelating agent, a more excellent coordination effect can be achieved with the first organic base, thereby further improving the final etching effect.

[0067] Among them, the first inorganic acid includes one or a combination of at least two of nitric acid, sulfuric acid, or phosphoric acid.

[0068] Exemplarily, the combinations of the first inorganic acid used are as follows: a combination of nitric acid and sulfuric acid, a combination of sulfuric acid and phosphoric acid, a combination of phosphoric acid and nitric acid.

[0069] In the present invention, the mass concentration of sulfuric acid used in the first inorganic acid is ≥98%, the mass concentration of nitric acid is ≥70%, and the mass concentration of phosphoric acid is ≥85%.

[0070] Among them, the first organic base includes one or a combination of at least two of triethanolamine, isopropanolamine, or triisopropanolamine.

[0071] In the present invention, the combinations of the first organic base used are as follows: a combination of triethanolamine and isopropanolamine, a combination of isopropanolamine and triisopropanolamine, a combination of triethanolamine and triisopropanolamine, a combination of triethanolamine, isopropanolamine, and triisopropanolamine, etc.

[0072] In the present invention, the first inorganic base includes ammonia water with a mass concentration ≤10%. For example, it can be 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, or 1%, etc., but is not limited to the listed values, and other unlisted values within this range also meet the requirements.

[0073] Among them, the first ether alcohol includes one or a combination of at least two of diethylene glycol butyl ether, ethylene glycol butyl ether, or glycerol monomethyl ether.

[0074] In the present invention, the combinations of the first alcohol ether used include: a combination of diethylene glycol butyl ether and ethylene glycol butyl ether, a combination of ethylene glycol butyl ether and glycerol monomethyl ether, a combination of diethylene glycol butyl ether, ethylene glycol butyl ether, and glycerol monomethyl ether, etc.

[0075] Among them, the first corrosion inhibitor includes one or a combination of at least two of methyl azole corrosion inhibitors, amino azole corrosion inhibitors, or pyridine-3-carboxylic acid.

[0076] In the present invention, the methyl azole corrosion inhibitors used include one or a combination of at least two of 5-methyltetrazole, 3-methyltetrazole, or 4-methyltriazole.

[0077] In the present invention, the amino azole corrosion inhibitors used include one or a combination of at least two of 5-aminotetrazole, 3-aminotetrazole, 4-aminotetrazole, or 5-aminotetrazole.

[0078] In the present invention, the combination of the first corrosion inhibitors used includes: the combination of methyl azole corrosion inhibitors and amino azole corrosion inhibitors, the combination of amino azole corrosion inhibitors and pyridine-3-carboxylic acid, the combination of methyl azole corrosion inhibitors and pyridine-3-carboxylic acid, and the combination of methyl azole corrosion inhibitors, amino azole corrosion inhibitors and pyridine-3-carboxylic acid.

[0079] In the present invention, by preferably configuring the combination of 5-amino tetrazole and pyridine-3-carboxylic acid with a mass ratio of (0.1 - 0.2):(0.01 - 0.02) in the first corrosion inhibitor, it can ensure that within the service life of the chemical solution, the etching characteristics are extremely stable, especially the variation in CD / Taper is very small, far exceeding the specification requirements, and ensuring the stable progress of the etching process.

[0080] Among them, the purine compounds include: one or a combination of at least two of purine, adenine, 2-aminopurine guanine, 7-deazaguanine or hypoxanthine.

[0081] In the present invention, the combinations of purine compounds used include: the combination of purine and adenine, the combination of 2-aminopurine guanine and 7-deazaguanine, the combination of adenine, 2-aminopurine guanine and hypoxanthine, the combination of purine, adenine and 2-aminopurine guanine, etc.

[0082] Among them, the etching solution for the copper molybdenum film layer further includes: an etching adjuvant; the raw materials of the etching adjuvant include, by weight:

[0083] 20 - 40 parts of a second organic acid chelating agent, 1 - 5 parts of a second inorganic acid, 10 - 20 parts of a second organic base, 1 - 2 parts of a second inorganic base, 1 - 3 parts of a second ether alcohol, 1 - 2 parts of a second corrosion inhibitor, and 40 - 50 parts of water.

[0084] In the present invention, for the raw materials of the etching adjuvant, the second organic acid chelating agent is 20 - 40 parts by weight, for example, it can be 20 parts, 22 parts, 24 parts, 26 parts, 28 parts, 30 parts, 32 parts, 34 parts, 36 parts, 38 parts or 40 parts, etc., but is not limited to the listed values, and other unlisted values within this range also meet the requirements.

[0085] In the present invention, for the raw materials of the etching adjuvant, the second inorganic acid is 1 - 5 parts by weight, for example, it can be 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts or 5 parts, etc., but is not limited to the listed values, and other unlisted values within this range also meet the requirements.

[0086] In the present invention, for the raw materials of the etching auxiliary agent, the second organic base is 10 - 20 parts by weight. For example, it can be 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts or 20 parts, etc., but not limited to the listed values. Other unlisted values within this range also meet the requirements.

[0087] In the present invention, for the raw materials of the etching auxiliary agent, the second inorganic base is 1 - 2 parts by weight. For example, it can be 1 part, 1.2 parts, 1.4 parts, 1.6 parts, 1.8 parts or 2 parts, etc., but not limited to the listed values. Other unlisted values within this range also meet the requirements.

[0088] In the present invention, for the raw materials of the etching auxiliary agent, the second ether alcohol is 1 - 3 parts by weight. For example, it can be 1 part, 1.2 parts, 1.4 parts, 1.6 parts, 1.8 parts, 2 parts, 2.2 parts, 2.4 parts, 2.6 parts, 2.8 parts or 3 parts, etc., but not limited to the listed values. Other unlisted values within this range also meet the requirements.

[0089] In the present invention, for the raw materials of the etching auxiliary agent, the second corrosion inhibitor is 1 - 2 parts by weight. For example, it can be 1 part, 1.1 parts, 1.2 parts, 1.3 parts, 1.4 parts, 1.5 parts, 1.6 parts, 1.7 parts, 1.8 parts, 1.9 parts or 2 parts, etc., but not limited to the listed values. Other unlisted values within this range also meet the requirements.

[0090] In the present invention, for the raw materials of the etching auxiliary agent, water is 40 - 50 parts by weight. For example, it can be 40 parts, 41 parts, 42 parts, 43 parts, 44 parts, 45 parts, 46 parts, 47 parts, 48 parts, 49 parts or 50 parts, etc., but not limited to the listed values. Other unlisted values within this range also meet the requirements.

[0091] Among them, the second organic acid chelating agent includes: a combination of at least 3 of citric acid, malonic acid, acetic acid or phenolsulfonic acid.

[0092] Exemplarily, the combinations of the second organic acid chelating agents used include: a combination of citric acid, malonic acid and acetic acid with a mass ratio of (3 - 5):1:1, a combination of malonic acid, acetic acid and phenolsulfonic acid with a mass ratio of (1.5 - 3):1:1, a combination of citric acid, malonic acid and phenolsulfonic acid with a mass ratio of (9 - 11):3:1, a combination of citric acid, acetic acid and phenolsulfonic acid with a mass ratio of (3.5 - 4.5):2:1 or a combination of citric acid, malonic acid, acetic acid and phenolsulfonic acid with a mass ratio of (3 - 5):2:1:1, etc.

[0093] Among them, the second inorganic acid includes: one or a combination of at least two of nitric acid, sulfuric acid or phosphoric acid.

[0094] Exemplarily, the combinations of the second inorganic acids used are as follows: combinations of nitric acid and sulfuric acid, combinations of sulfuric acid and phosphoric acid, combinations of nitric acid and phosphoric acid, combinations of nitric acid, sulfuric acid and phosphoric acid, etc.

[0095] In the present invention, the mass concentration of sulfuric acid used in the second inorganic acid is ≥98%, the mass concentration of nitric acid is ≥70%, and the mass concentration of phosphoric acid is ≥85%.

[0096] Among them, the second organic base includes: one or a combination of at least two of triethanolamine, isopropanolamine or triisopropanolamine.

[0097] Exemplarily, the combinations of the second organic bases used are as follows: combinations of triethanolamine and isopropanolamine, combinations of isopropanolamine and triisopropanolamine, combinations of triethanolamine and triisopropanolamine, combinations of triethanolamine, isopropanolamine and triisopropanolamine, etc.

[0098] In the present invention, the second inorganic base includes: ammonia water with a mass concentration ≤10%, for example, it can be 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2% or 1%, etc., but not limited to the listed values, and other unlisted values within this range also meet the requirements.

[0099] Among them, the second ether alcohol includes: one or a combination of at least two of diethylene glycol butyl ether, ethylene glycol butyl ether or glycerol monomethyl ether.

[0100] Exemplarily, the combinations of the second ether alcohols used are as follows: combinations of diethylene glycol butyl ether and ethylene glycol butyl ether, combinations of ethylene glycol butyl ether and glycerol monomethyl ether, combinations of diethylene glycol butyl ether, ethylene glycol butyl ether and glycerol monomethyl ether, etc.

[0101] Among them, the second corrosion inhibitor includes: one or a combination of at least two of methyl azole corrosion inhibitors, amino azole corrosion inhibitors or pyridine-3-carboxylic acid.

[0102] Exemplarily, the combinations of the first corrosion inhibitors used include: combinations of methyl azole corrosion inhibitors and amino azole corrosion inhibitors, combinations of amino azole corrosion inhibitors and pyridine-3-carboxylic acid, combinations of methyl azole corrosion inhibitors and pyridine-3-carboxylic acid, combinations of methyl azole corrosion inhibitors, amino azole corrosion inhibitors and pyridine-3-carboxylic acid.

[0103] In the present invention, the preparation of the foregoing etching main agent and etching auxiliary agent can be formulated according to the formula and then obtained by mixing.

[0104] Furthermore, the present embodiment provides an etching method based on the foregoing etching solution, and the etching method includes:

[0105] Etching the copper-molybdenum film layer with the etching main agent;

[0106] Among them, for every 1000 ppm increase in copper ions in the liquid phase during the etching, an etching adjuvant accounting for 1-1.2% of the mass of the main etching agent is added. For example, it can be 1%, 1.02%, 1.04%, 1.06%, 1.08%, 1.1%, 1.12%, 1.14%, 1.16%, 1.18% or 1.2%, etc., but not limited to the listed values. Other unlisted values within this range also meet the requirements.

[0107] Among them, the temperature of the etching is 25-40 °C. For example, it can be 25 °C, 26 °C, 27 °C, 28 °C, 29 °C, 30 °C, 32 °C, 34 °C, 36 °C, 38 °C or 40 °C, etc., but not limited to the listed values. Other unlisted values within this range also meet the requirements.

[0108] Furthermore, in order to illustrate the etching effect that can be achieved by the etching solution provided by the present invention for the copper molybdenum film layer, the following actual examples are used, and the specific description is as follows:

[0109] Example 1

[0110] This example provides an etching solution for a copper molybdenum film layer, including: a main etching agent and an etching adjuvant;

[0111] The raw materials of the main etching agent include, by weight:

[0112] 10 parts of an oxidizing agent (hydrogen peroxide, mass concentration of 31%), 7 parts of a first organic acid chelating agent (p-phenolsulfonic acid), 2.5 parts of a first inorganic acid (nitric acid, mass concentration of 70%), 8 parts of a first organic base (triethanolamine), 0.6 parts of a first inorganic base (ammonia water, mass concentration of 8%), 1 part of a first ether alcohol (diethylene glycol butyl ether), 0.03 parts of a first corrosion inhibitor (amino azole corrosion inhibitor: 5-aminotetrazole), 0.03 parts of a purine compound (adenine), and 75 parts of water;

[0113] The raw materials of the etching adjuvant include, by weight:

[0114] 30 parts of a second organic acid chelating agent (citric acid, malonic acid and acetic acid with a mass ratio of 4:1:1), 3 parts of a second inorganic acid (sulfuric acid, mass concentration of 98%), 15 parts of a second organic base (triethanolamine), 1.6 parts of a second inorganic base (ammonia water, mass concentration of 5%), 2.5 parts of a second ether alcohol (diethylene glycol butyl ether), 1.5 parts of a second corrosion inhibitor (amino azole corrosion inhibitor: 3-aminotetrazole), and 45 parts of water.

[0115] Example 2

[0116] This example provides an etching solution for a copper molybdenum film layer, including: a main etching agent and an etching adjuvant;

[0117] The raw materials of the main etching agent include, by weight:

[0118] Oxidant (hydrogen peroxide, mass concentration 25%) 10.5 parts, first organic acid chelating agent (meta-phenolsulfonic acid and malonic acid with a mass ratio of 1:1) 6 parts, first inorganic acid (phosphoric acid, mass concentration 85%) 2 parts, first organic base (triethanolamine and isopropanolamine with a mass ratio of 1:1) 9 parts, first inorganic base (ammonia water, mass concentration 10%) 0.8 part, first ether alcohol (glycerol monomethyl ether) 1.5 parts, first corrosion inhibitor (methyl azole corrosion inhibitor: 5-methyltetrazole) 0.02 part, purine compound (purine) 0.04 part, water 78 parts;

[0119] The raw materials of the auxiliary etching agent include, by weight:

[0120] Second organic acid chelating agent (citric acid, acetic acid and o-phenolsulfonic acid with a mass ratio of 4:2:1) 40 parts, second inorganic acid (phosphoric acid, mass concentration 85%) 4 parts, second organic base (triethanolamine) 18 parts, second inorganic base (ammonia water, mass concentration 6%) 1.4 parts, second ether alcohol (glycerol monomethyl ether) 2 parts, second corrosion inhibitor (methyl azole corrosion inhibitor, 3-methyltetrazole) 1.5 parts, water 45 parts.

[0121] Example 3

[0122] This example provides an etching solution for a copper-molybdenum film layer, including: a main etching agent and an auxiliary etching agent;

[0123] The raw materials of the main etching agent include, by weight:

[0124] Oxidant (sodium persulfate) 11 parts, first organic acid chelating agent (acetic acid, malonic acid, malic acid and p-phenolsulfonic acid with a mass ratio of 1:2:1:2) 8 parts, first inorganic acid (nitric acid, mass concentration 70%) 1 part, first organic base (triisopropanolamine) 10 parts, first inorganic base (ammonia water, mass concentration 10%) 0.5 part, first ether alcohol (glycerol monomethyl ether) 0.5 part, first corrosion inhibitor (pyridine-3-carboxylic acid) 0.05 part, purine compound (2-aminopurine guanine) 0.01 part, water 70 parts;

[0125] The raw materials of the auxiliary etching agent include, by weight:

[0126] Second organic acid chelating agent (citric acid, malonic acid and m-phenolsulfonic acid with a mass ratio of 10:3:1) 20 parts, second inorganic acid (phosphoric acid, mass concentration 90%) 5 parts, second organic base (triethanolamine) 10 parts, second inorganic base (ammonia water, mass concentration 10%) 1 part, second ether alcohol (ethylene glycol monobutyl ether) 1 part, second corrosion inhibitor (pyridine-3-carboxylic acid) 2 parts, water 50 parts.

[0127] Example 4

[0128] This example provides an etching solution for a copper-molybdenum film layer, including: an etching main agent and an etching auxiliary agent;

[0129] The raw materials of the etching main agent include, by weight:

[0130] 9 parts of an oxidant (ammonium persulfate), 5 parts of a first organic acid chelating agent (acetic acid, malonic acid, citric acid, and p-phenolsulfonic acid with a mass ratio of 1:2:1:2), 3 parts of a first inorganic acid (phosphoric acid, with a mass concentration of 95%), 6 parts of a first organic base (isopropanolamine), 1 part of a first inorganic base (ammonia water, with a mass concentration of 5%), 2 parts of a first ether alcohol (diethylene glycol butyl ether), 0.01 part of a first corrosion inhibitor (pyridine-3-carboxylic acid), 0.05 part of a purine compound (adenine), and 80 parts of water;

[0131] The raw materials of the etching auxiliary agent include, by weight:

[0132] 40 parts of a second organic acid chelating agent (malonic acid, acetic acid, and o-phenolsulfonic acid with a mass ratio of 2:1:1), 1 part of a second inorganic acid (sulfuric acid, with a mass concentration of 98%), 20 parts of a second organic base (isopropanolamine), 2 parts of a second inorganic base (ammonia water, with a mass concentration of 5%), 3 parts of a second ether alcohol (glycerol monomethyl ether), 1 part of a second corrosion inhibitor (pyridine-3-carboxylic acid), and 40 parts of water.

[0133] Example 5

[0134] The difference from Example 1 is only that the first organic acid chelating agent (p-phenolsulfonic acid) is replaced with an equal amount of p-phenolsulfonic acid and malonic acid with a mass ratio of 1:1.

[0135] Example 6

[0136] The difference from Example 1 is only that the first organic acid chelating agent (p-phenolsulfonic acid) is replaced with an equal amount of p-phenolsulfonic acid and malic acid with a mass ratio of 2:1.

[0137] Example 7

[0138] The difference from Example 1 is only that the first organic acid chelating agent (p-phenolsulfonic acid) is replaced with an equal amount of acetic acid, malonic acid, malic acid, and p-phenolsulfonic acid with a mass ratio of 1:2:1:2.

[0139] Example 8

[0140] The difference from Example 1 is only that the first organic acid chelating agent (p-phenolsulfonic acid) is replaced with an equal amount of acetic acid, malonic acid, citric acid, and p-phenolsulfonic acid with a mass ratio of 1:2:1:2.

[0141] Example 9

[0142] The difference from Example 1 is only that the first organic base (triethanolamine) is replaced with an equal amount of triethanolamine and isopropanolamine with a mass ratio of 1:1.

[0143] Example 10

[0144] The difference from Example 1 is only that the first inorganic acid (nitric acid) is replaced with an equal amount of phosphoric acid (mass concentration: 85%).

[0145] Example 11

[0146] The difference from Example 1 is only that the first corrosion inhibitor (amino azole corrosion inhibitor) is replaced with 5 - aminotetrazole and pyridine - 3 - carboxylic acid with a mass ratio of 1:0.1.

[0147] Example 12

[0148] The difference from Example 1 is only that the second organic acid chelating agent (citric acid, malonic acid and acetic acid with a mass ratio of 4:1:1) is replaced with an equal amount of citric acid, malonic acid, acetic acid and phenolsulfonic acid with a mass ratio of 4:2:1:1.

[0149] Comparative Example 1

[0150] The difference from Example 3 is only that phenolsulfonic acid in the first organic acid chelating agent is replaced with an equal amount of benzenesulfonic acid.

[0151] Comparative Example 2

[0152] The difference from Example 3 is only that phenolsulfonic acid in the first organic acid chelating agent is replaced with an equimolar amount of sulfuric acid.

[0153] Comparative Example 3

[0154] The difference from Example 3 is only that the first organic base is replaced with an equal amount of sodium hydroxide.

[0155] Comparative Example 4

[0156] The difference from Example 3 is only that the first alcohol ether is not added.

[0157] Comparative Example 5

[0158] The difference from Example 3 is only that the first alcohol ether is replaced with an equal amount of butyl ether.

[0159] Comparative Example 6

[0160] The difference from Example 3 is only that the first alcohol ether is replaced with an equal amount of fatty alcohol polyoxyethylene ether AEO - 9.

[0161] Comparative Example 7

[0162] The difference from Example 3 is only that the purine compound is replaced with an equal amount of uracil.

[0163] Comparative Example 8

[0164] It is only different from Example 3 in that no purine compound is added.

[0165] Comparative Example 9

[0166] It is only different from Example 3 in that the weight part of the first organic acid chelating agent is 2 parts.

[0167] Comparative Example 10

[0168] It is only different from Example 3 in that the weight part of the first organic acid chelating agent is 10 parts.

[0169] Comparative Example 11

[0170] It is only different from Example 3 in that the weight part of the first organic base is 4 parts.

[0171] Comparative Example 12

[0172] It is only different from Example 3 in that the weight part of the first organic base is 15 parts.

[0173] Comparative Example 13

[0174] It is only different from Example 3 in that the weight part of the first ether alcohol is 0.1 part.

[0175] Comparative Example 14

[0176] It is only different from Example 3 in that the weight part of the first ether alcohol is 3 parts.

[0177] Comparative Example 15

[0178] It is only different from Example 3 in that the weight part of the purine compound is 0.005 part.

[0179] Comparative Example 16

[0180] It is only different from Example 3 in that the weight part of the purine compound is 0.1 part.

[0181] Using the etching solutions provided in the above examples and comparative examples for copper-molybdenum film layer and copper-molybdenum film layer are etched at 25 °C respectively. For every 1000 ppm increase in copper ions in the liquid phase during etching, an etching adjuvant accounting for 1% of the mass of the etching main agent is added. After etching, tests are carried out. The results are shown in Table 1 below. Among them, the SEM photograph of the product obtained after etching the copper-molybdenum film layer in Example 1 is as shown in Figure 1 shown.

[0182] Table 1

[0183]

[0184]

[0185] As can be seen from Table 1, the etching solution provided by the present invention can achieve excellent chamfers and remaining spaces when etching copper-molybdenum film layers with different thickness ratios by virtue of the synergistic effect of organic acids, inorganic acids, and inorganic bases, which is beneficial to the efficient preparation of display panels.

[0186] The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited to the specific details in the above embodiments. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solutions of the present invention, and these simple modifications all fall within the protection scope of the present invention.

[0187] In addition, it should be noted that, in the case of no contradiction, the various specific technical features described in the above specific embodiments can be combined in any appropriate manner. To avoid unnecessary repetition, the present invention will not separately describe various possible combination methods.

[0188] In addition, any combination can be made between various different embodiments of the present invention as long as it does not violate the idea of the present invention, and it should also be regarded as the content disclosed by the present invention.

Claims

1. An etching solution for copper-molybdenum film layer, characterized in that: The etching solution for the copper-molybdenum film layer comprises: an etching main agent; The raw materials of the etching agent include, by weight: 9-11 parts of oxidant, 5-8 parts of first organic acid chelating agent, 1-3 parts of first inorganic acid, 6-10 parts of first organic base, 0.5-1 parts of first inorganic base, 0.5-2 parts of first ether alcohol, 0.01-0.05 parts of first corrosion inhibitor, 0.01-0.05 parts of purine compound, 70-80 parts of water; Wherein, the first organic acid chelating agent includes phenolsulfonic acid.

2. The etching solution for copper-molybdenum film layer according to claim 1, characterized in that: The oxidant includes: hydrogen peroxide and / or persulfate; Preferably, the first organic acid chelating agent further comprises: one or a combination of at least two of malonic acid, malic acid, citric acid or acetic acid; Preferably, the first organic acid chelating agent includes: acetic acid, malonic acid, malic acid and phenolsulfonic acid.

3. The etching solution for copper-molybdenum film layer according to claim 1 or 2, characterized in that: The first inorganic acid comprises: one or a combination of at least two of nitric acid, sulfuric acid or phosphoric acid; Preferably, the first organic base comprises: one or a combination of at least two of triethanolamine, isopropanolamine or triisopropanolamine; Preferably, the first inorganic base comprises: aqueous ammonia with a mass concentration of ≤10%.

4. The etching solution for copper-molybdenum film layer according to any one of claims 1 to 3, characterized in that: The first ether alcohol comprises: one or a combination of at least two of diethylene glycol butyl ether, ethylene glycol butyl ether or glycerol monomethyl ether; Preferably, the first corrosion inhibitor comprises: one or a combination of at least two of a methyl nitrogen azole corrosion inhibitor, an amino nitrogen azole corrosion inhibitor or pyridine-3-carboxylic acid; Preferably, the purine compound comprises: one or a combination of at least two of purine, adenine, 2-aminopurine guanine, 7-deazaadenine or hypoxanthine.

5. The etching solution for copper-molybdenum film layer according to any one of claims 1 to 4, characterized in that: The etching solution for the copper-molybdenum film layer also includes: an etching auxiliary agent; The raw materials of the etching auxiliary agent include, by weight: 20-40 parts of the second organic acid chelating agent, 1-5 parts of the second inorganic acid, 10-20 parts of the second organic base, 1-2 parts of the second inorganic base, 1-3 parts of the second ether alcohol, 1-2 parts of the second corrosion inhibitor, and 40-50 parts of water.

6. The etching solution for copper-molybdenum film layer according to claim 5, characterized in that: The second organic acid chelating agent comprises: a combination of at least three of citric acid, malonic acid, acetic acid or phenolsulfonic acid; Preferably, the second organic acid chelating agent comprises: a combination of citric acid, malonic acid and acetic acid in a mass ratio of (3-5):1:1, a combination of malonic acid, acetic acid and phenolsulfonic acid in a mass ratio of (1.5-3):1:1, a combination of citric acid, malonic acid and phenolsulfonic acid in a mass ratio of (9-11):3:1, a combination of citric acid, acetic acid and phenolsulfonic acid in a mass ratio of (3.5-4.5):2:1, or a combination of citric acid, malonic acid, acetic acid and phenolsulfonic acid in a mass ratio of (3-5):2:1:1; Preferably, the second inorganic acid comprises: one or a combination of at least two of nitric acid, sulfuric acid or phosphoric acid; Preferably, the second organic base comprises: one or a combination of at least two of triethanolamine, isopropanolamine or triisopropanolamine; Preferably, the second inorganic base comprises: aqueous ammonia with a mass concentration of ≤10%.

7. The etching solution for copper-molybdenum film layer according to claim 5 or 6, characterized in that: The second ether alcohol comprises: one or a combination of at least two of diethylene glycol butyl ether, ethylene glycol butyl ether or glycerol monomethyl ether; Preferably, the second corrosion inhibitor comprises: one or a combination of at least two of methyl nitrogen azole corrosion inhibitor, amino nitrogen azole corrosion inhibitor or pyridine-3-carboxylic acid.

8. An etching method for a copper-molybdenum film layer, characterized in that: The etching method comprises: etching the copper-molybdenum film layer using the etching solution as described in any one of claims 1-7.

9. The etching method according to claim 8, characterized in that: The etching method comprises: Etching the copper-molybdenum film layer using the etching agent; Wherein, for every 1000 ppm increase in copper ions in the liquid phase during etching, 1-1.2% of the mass of the etching main agent is added as an etching auxiliary agent.

10. The etching method according to claim 8 or 9, characterized in that: The etching temperature is 25-40°C.

Images