TFT-LCD wet process high-speed copper etching liquid and application thereof

Abstract

The invention relates to the field of etching solutions, and discloses a TFT-LCD wet process high-speed copper etching solution and application thereof, the etching solution comprises a main etching agent and a supplement; the main etching agent comprises 10 to 15 weight percent of hydrogen peroxide, 2.8 to 3.8 weight percent of first organic alkali, 2.71 to 5.9 weight percent of first organic acid, 0.001 to 0.01 weight percent of corrosion inhibitor, 0.01 to 0.2 weight percent of hydrogen peroxide stabilizer, 0.1 to 2 weight percent of pH regulator and the balance of deionized water; and the supplement comprises 15-44 wt% of a second organic alkali, 15-35 wt% of a second organic acid, 0.5-2 wt% of a hydrogen peroxide stabilizer, 0.01-0.2 wt% of a corrosion inhibitor, 3-10 wt% of a third organic acid and the balance of deionized water. The etching solution is environment-friendly, free of pollution, high in etching speed, uniform and stable in etching angle, free of undercutting, drilling, metal residues and the like, and high in copper dissolving amount.

Description

Technical Field

[0001] The present application belongs to the technical field of copper etching solutions for liquid crystal panels, and in particular relates to a high-speed copper etching solution for a TFT-LCD wet process and its application. Background Art

[0002] The microcircuits of thin-film transistor liquid crystal displays (TFT-LCDs) are formed through a series of exposure and development processes. Specifically, a photoresist (PR) is evenly coated on the metal / semiconductor / insulating films formed on the substrate. After exposure to light, the film is developed to form a patterned photoresist. Dry or wet etching is then used to remove the portions not covered by the photoresist. Finally, the PR is peeled off to form a patterned film layer. This process repeats over and over again to form the microcircuit. In the field of TFT-LCD panels, there are two main metallization processes: aluminum and copper. Compared to aluminum, the core of the copper process is to replace the metal traces of the gate and SD source and drain electrodes in the TFT array substrate with copper. Copper has high conductivity and low resistivity, which can significantly reduce signal delay and facilitate the development of TFT-LCD panels in larger sizes, higher resolutions, higher refresh rates, and higher transmittance. Considering the poor adhesion between copper and glass substrates, which may cause the Cu film to fall off or break during subsequent processing, a buffer metal layer is deposited between them to prevent Cu diffusion. Currently, molybdenum and its alloys (such as MoNb and MoTi) are attracting much attention.

[0003] To effectively etch this multilayer metal film, the industry generally uses hydrogen peroxide-based copper etching solutions. High-performance etching solutions should have a suitable bond size loss (CD Loss), a large etching coefficient, low side etching, stable etching performance, excellent copper dissolving ability, and easy disposal of copper etching wastewater. However, in the prior art, fluorine-containing etching solutions are commonly used to improve the etching effect on metal molybdenum. However, fluorine-containing etching solutions increase the difficulty and cost of handling copper etching wastewater and cause environmental pollution. At the same time, existing etching solutions are also prone to producing inappropriate taper angles, resulting in poor etching. Too large an angle can easily lead to fractures and metal disconnection during deposition of the next metal film, affecting product performance; too small an angle causes thermal expansion and contraction deformation, affecting the direction and precision of metal wiring. Furthermore, although some hydrogen peroxide-based copper etching solutions in the prior art can have a service life of up to 8,000-10,000 ppm, their etching rates are too slow and the etching process is unstable, resulting in poor CD Loss uniformity, as well as chamfers and cracks. Summary of the Invention

[0004] Based on the above deficiencies in the prior art, the present invention provides a TFT-LCD wet process high-speed copper etching solution and its application, which has the advantages of fast etching rate, stable etching reaction, good etching effect, and long service life.

[0005] To achieve the above application objectives, the technical solutions adopted in this application are as follows:

[0006] In a first aspect, the present application provides a high-speed copper etching solution for a TFT-LCD wet process, the copper etching solution comprising a main etchant and a supplement;

[0007] The main etchant comprises the following components by mass percentage: 10% to 15% of hydrogen peroxide, 2.8% to 3.8% of a first organic base, 2.71% to 5.9% of a first organic acid, 0.001% to 0.01% of a corrosion inhibitor, 0.01% to 0.2% of a hydrogen peroxide stabilizer, 0.1% to 2% of a pH regulator, and the balance being deionized water;

[0008] The supplement comprises the following components in percentage by mass: 15% to 44% of a second organic base, 15% to 35% of a second organic acid, 0.5% to 2% of a hydrogen peroxide stabilizer, 0.01% to 0.2% of a corrosion inhibitor, 3% to 10% of a third organic acid, and the balance being deionized water.

[0009] As a possible design, the first organic acid includes malonic acid, citric acid and malic acid; the mass percentage of malonic acid in the main etchant is 0.7% to 1.7%, the mass percentage of citric acid is 2% to 4%, and the mass percentage of malic acid is 0.01% to 0.2%.

[0010] As a possible design, the second organic base includes 3-diethylaminopropylamine and triisopropanolamine; the mass percentage of 3-diethylaminopropylamine in the supplement is 10% to 25%, and the mass percentage of triisopropanolamine is 5% to 19%.

[0011] As a possible design, the first organic base is 3-diethylaminopropylamine; the corrosion inhibitor is 5-aminotetrazole; the hydrogen peroxide stabilizer is phenylurea; and the pH adjuster is nitric acid.

[0012] As a possible design, the second organic acid is citric acid; and the third organic acid is malonic acid.

[0013] As a possible design, the main etchant includes the following components by mass percentage: 10% to 15% hydrogen peroxide, 2.8% to 3.8% 3-diethylaminopropylamine, 0.7% to 1.7% malonic acid, 2% to 4% citric acid, 0.01% to 0.2% malic acid, 0.001% to 0.01% 5-aminotetrazole, 0.01% to 0.2% phenylurea, 0.1% to 2% nitric acid, and the balance is deionized water;

[0014] The supplement comprises the following components in percentage by mass: 10% to 25% of 3-diethylaminopropylamine, 5% to 19% of triisopropanolamine, 15% to 35% of citric acid, 0.5% to 2% of phenylurea, 0.01% to 0.2% of 5-aminotetrazole, 3% to 10% of malonic acid, and the balance is deionized water.

[0015] As a possible design, the main etchant includes the following components by mass percentage: 12.50% hydrogen peroxide, 3.3% 3-diethylaminopropylamine, 1.2% malonic acid, 3.00% citric acid, 0.05% malic acid, 0.008% 5-aminotetrazole, 0.08% phenylurea, 1.00% nitric acid, and the balance is deionized water;

[0016] The supplement comprises the following components in percentage by mass: 16.80% of 3-diethylaminopropylamine, 9% of triisopropanolamine, 26% of citric acid, 1.28% of phenylurea, 0.08% of 5-aminotetrazole, 6.4% of malonic acid, and the balance is deionized water.

[0017] In a second aspect, the present invention provides a method for etching a film layer containing copper, wherein the etching is performed by contacting the etching solution with the object to be etched. Preferably, during the etching process, for every 1000 ppm increase in the copper ion concentration in the etching solution, an extender is added at a ratio of 0.1 to 13.4 wt% of the main etchant. In practice, the higher the copper ion concentration, the higher the proportion of the extender added.

[0018] In a third aspect, the present invention provides a use of the aforementioned etching solution in etching a liquid crystal panel having an oxide liquid crystal panel and a copper / molybdenum multilayer thin film.

[0019] As a possible design, the copper / molybdenum multilayer film includes a Cu / MoNb Gate multilayer and / or a Cu / MoNb SD multilayer; preferably, the Cu / MoNb Gate multilayer includes a GT GT GT and GT At least one; preferably, the Cu / MoNb SD multi-layer includes SD and / or SD

[0020] The beneficial effects of the present invention are as follows:

[0021] 1. Free of fluorine, phosphorus and sulfur ions, environmentally friendly and pollution-free.

[0022] 2. Compatible with multiple substrates at the same time: such as Cu / MoNb Gate multi-layer thickness (GT GT GT and GT ) and Cu / MoNb SD multi-layer thickness (SD and SD ).

[0023] 3. Fast etching speed, uniform and stable etching angle TaperCD loss, no undercut, drilling, metal residue, etc., high copper dissolution capacity and long service life. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the following briefly introduces the drawings required for use in the embodiments or descriptions of the prior art. Obviously, the drawings described below are only some embodiments of the present application. For ordinary technicians in this field, other drawings can be obtained based on these drawings without any creative work.

[0025] Figure 1 The etching solution provided in Example 1 of the present application is in SD Etching angle diagram with the highest dissolved copper content on the film layer being 11000ppm;

[0026] Figure 2 The etching solution provided in Example 1 of the present application is in GT Etching angle diagram with the highest dissolved copper content on the film layer being 11000ppm;

[0027] Figure 3 The etching solution provided in Example 1 of the present application is in GT Etching angle diagram with the highest dissolved copper content on the film layer being 11000ppm;

[0028] Figure 4 The etching solution provided in Example 1 of the present application is in GT Etching angle diagram with the highest dissolved copper content on the film layer being 11000ppm;

[0029] Figure 5 The etching solution provided in Example 1 of the present application is in SD Etching angle diagram with the highest dissolved copper content on the film layer being 11000ppm;

[0030] Figure 6 The etching solution provided in Example 1 of the present application is in GT Etching angle diagram with the highest dissolved copper content on the film layer being 11000ppm;

[0031] Figure 7 The etching solution provided in Example 2 of the present application is in SD Etching angle diagram with the highest dissolved copper content on the film layer being 11000ppm;

[0032] Figure 8 The etching solution provided in Example 3 of the present application is in SD Etching angle diagram with the highest dissolved copper content on the film layer being 11000ppm;

[0033] Figure 9 The etching solution provided in Example 4 of the present application is in GT Etching angle diagram with the highest dissolved copper content on the film layer being 11000ppm;

[0034] Figure 10 The etching solution provided in Example 5 of the present application is in GT Etching angle diagram with the highest dissolved copper content on the film layer being 11000ppm;

[0035] Figure 11 The etching solution provided in Example 6 of the present application is in GT Etching angle diagram with the highest dissolved copper content on the film layer being 11000ppm;

[0036] Figure 12 The etching solution provided in Example 7 of the present application is in SD Etching angle diagram with the highest dissolved copper content on the film layer being 11000ppm;

[0037] Figure 13 The etching solution provided in Comparative Example 1 of this application is in SD Etching angle diagram with the highest dissolved copper content on the film layer being 8000ppm;

[0038] Figure 14 The etching solution provided in Comparative Example 1 of this application is in GT Etching angle diagram with the highest dissolved copper content on the film layer being 8000ppm;

[0039] Figure 15 The etching solution provided in Comparative Example 2 of this application is in SD Etching angle diagram with the highest dissolved copper content on the film layer being 10,000 ppm;

[0040] Figure 16 The etching solution provided in Comparative Example 3 of this application is in GT Etching angle diagram with the highest dissolved copper content on the film layer being 8000ppm;

[0041] Figure 17 The etching solution provided in Comparative Example 4 of this application is in GT Etching angle diagram with the highest dissolved copper content on the film layer being 8000ppm;

[0042] Figure 18 The etching solution provided in Comparative Example 5 of this application is in SD Etching angle diagram with the highest dissolved copper content of 6000ppm on the film layer;

[0043] Figure 19 The etching solution provided in Comparative Example 6 of this application is in GT Etching angle diagram with the highest dissolved copper content on the film layer being 8000ppm;

[0044] Figure 20 The etching solution provided in Comparative Example 7 of this application is in GT Etching angle diagram with the highest dissolved copper content of 6000ppm on the film layer;

[0045] Figure 21 The etching solution provided in Comparative Example 8 of this application is in SD Etching angle diagram with the highest dissolved copper content of 6000ppm on the film layer;

[0046] Figure 22 The etching solution provided in Comparative Example 9 of this application is in SD Etching angle diagram with the highest dissolved copper content of 7500ppm on the film layer;

[0047] Figure 23 This is an etching angle diagram of the etching solution provided in Comparative Example 10 of the present application on the GT 6500 / / 150A film layer with a maximum copper dissolution amount of 8000 ppm;

[0048] Figure 24 The etching solution provided in Comparative Example 11 of this application is in SD Etching angle diagram with the highest dissolved copper content of 6000ppm on the film layer;

[0049] Figure 25 The etching solution provided in Comparative Example 12 of this application is in GT Etching angle diagram with the highest dissolved copper content on the film layer being 8000ppm;

[0050] Figure 26 The etching solution provided in Comparative Example 13 of this application is in GT Etching angle diagram with the highest dissolved copper content on the film layer being 8000ppm;

[0051] Figure 27 The etching solution provided in Example 1 of the present application is in SD The surface condition of the film after etching with the highest dissolved copper content of 11000ppm;

[0052] Figure 28 The etching solution provided in Comparative Example 9 of this application is in SD The surface condition of the film after etching with the highest dissolved copper content of 7500ppm. DETAILED DESCRIPTION

[0053] In order to make the technical problems, technical solutions and beneficial effects to be solved by this application more clearly understood, the present application is further described in detail below in conjunction with the embodiments. It should be understood that the specific embodiments described herein are only used to explain this application and are not intended to limit this application.

[0054] In this application, the term "and / or" describes the relationship between associated objects, indicating that three possible relationships exist. For example, A and / or B can represent: A exists alone, A and B exist simultaneously, and B exists alone. A and B can be singular or plural. The character " / " generally indicates that the associated objects are in an "or" relationship.

[0055] It should be understood that in the various embodiments of the present application, the size of the serial numbers of the above-mentioned processes does not mean the order of execution. Some or all of the steps can be executed in parallel or sequentially. The execution order of each process should be determined by its function and internal logic, and should not constitute any limitation on the implementation process of the embodiments of the present application.

[0056] The terms used in the embodiments of the present application are for the purpose of describing specific embodiments only and are not intended to limit the present application. The singular forms "a", "an", "the" and "the" used in the embodiments of the present application and the appended claims are also intended to include plural forms unless the context clearly indicates otherwise.

[0057] The weights of the relevant components mentioned in the examples of this application may not only refer to the specific content of each component, but also represent the weight ratio between the components. Therefore, as long as the content of the relevant components is proportionally enlarged or reduced according to the examples of this application, it is within the scope disclosed in the examples of this application. Specifically, the mass described in the examples of this application may be a mass unit known in the chemical industry, such as μg, mg, g, kg, etc.

[0058] The terms "first" and "second" are used solely for descriptive purposes to distinguish objects, such as substances, from one another and should not be construed as indicating or implying relative importance or implicitly specifying the quantity of the technical features being referred to. For example, a first XX could also be referred to as a second XX, and similarly, a second XX could also be referred to as a first XX, without departing from the scope of the embodiments of this application. Thus, features defined as "first" or "second" may explicitly or implicitly include one or more of such features.

[0059] The term "DEA" is the abbreviation of "3-diethylaminopropylamine"; the term "BS2" is the abbreviation of "malonic acid"; the term "NS" is the abbreviation of lemon; the term "DLS" is the abbreviation of malic acid; the term "DZ" is the abbreviation of 5-aminotetrazolyl; the term "BJN" is the abbreviation of phenylurea; the term "NF" is the abbreviation of ammonium fluoride; the term "TIPA" is the abbreviation of triisopropanolamine; the term "RS" is the abbreviation of lactic acid; the term "MEA" is the abbreviation of ethanolamine; and the term "IDA" is the abbreviation of iminodiacetic acid.

[0060] In the following embodiments and comparative examples, the addition ratio of the supplement (mass percentage of the main etchant) can be specifically as follows:

[0061] When the dissolved copper amount is 1000ppm, the addition ratio of the supplement is 0.6wt%; when the dissolved copper amount is 2000ppm, the addition ratio of the supplement is 1.8wt%; when the dissolved copper amount is 3000ppm, the addition ratio of the supplement is 3wt%; when the dissolved copper amount is 4000ppm, the addition ratio of the supplement is 4.2wt%; when the dissolved copper amount is 5000ppm, the addition ratio of the supplement is 5.4wt%; when the dissolved copper amount is 6000ppm, the addition ratio of the supplement is 6.6wt%; when the dissolved copper amount is 7000ppm, the addition ratio of the supplement is 8.3wt%; when the dissolved copper amount is 8000ppm, the addition ratio of the supplement is 10wt%; when the dissolved copper amount is 9000ppm, the addition ratio of the supplement is 11.2wt%; when the dissolved copper amount is 10000ppm, the addition ratio of the supplement is 13.4wt%.

[0062] Example 1

[0063] This embodiment discloses a high-speed copper etching solution for a TFT-LCD wet process, wherein the etching solution includes a main etching agent and a supplement;

[0064] The main etchant includes the following components by mass percentage: 12.50% hydrogen peroxide, 3.3% 3-diethylaminopropylamine, 1.2% malonic acid, 3.00% citric acid, 0.05% malic acid, 0.008% 5-aminotetrazole, 0.08% phenylurea, 1.00% nitric acid, and the balance is deionized water;

[0065] The supplement includes the following components in percentage by mass: 16.80% of 3-diethylaminopropylamine, 9% of triisopropanolamine, 26% of citric acid, 1.28% of phenylurea, 0.08% of 5-aminotetrazole, 6.4% of malonic acid, and the balance is deionized water.

[0066] The preparation method of the main etchant is to mix the raw materials uniformly. The preparation method of the supplement is to mix the raw materials uniformly.

[0067] Example 2

[0068] This embodiment discloses a high-speed copper etching solution for a TFT-LCD wet process, wherein the etching solution includes a main etching agent and a supplement;

[0069] The main etchant includes the following components by mass percentage: 10% hydrogen peroxide, 2.800% 3-diethylaminopropylamine, 0.700% malonic acid, 2.00% citric acid, 0.010% malic acid, 0.001% 5-aminotetrazole, 0.010% phenylurea, 0.1% nitric acid, and the balance is deionized water;

[0070] The supplement comprises the following components in percentage by mass: 10% of 3-diethylaminopropylamine, 5% of triisopropanolamine, 15% of citric acid, 0.500% of phenylurea, 0.010% of 5-aminotetrazole, 3% of malonic acid, and the balance is deionized water.

[0071] The preparation method of the main etchant is to mix the raw materials uniformly. The preparation method of the supplement is to mix the raw materials uniformly.

[0072] Example 3

[0073] This embodiment discloses a high-speed copper etching solution for a TFT-LCD wet process, wherein the etching solution includes a main etching agent and a supplement;

[0074] The main etchant includes the following components by mass percentage: 15% hydrogen peroxide, 3.8% 3-diethylaminopropylamine, 1.7% malonic acid, 4.00% citric acid, 0.200% malic acid, 0.010% 5-aminotetrazole, 0.200% phenylurea, 2.000% nitric acid, and the balance is deionized water;

[0075] The supplement comprises the following components in percentage by mass: 25.000% of 3-diethylaminopropylamine, 19.000% of triisopropanolamine, 35.000% of citric acid, 2.000% of phenylurea, 0.200% of 5-aminotetrazole, 10.000% of malonic acid, and the balance is deionized water.

[0076] The preparation method of the main etchant is to mix the raw materials uniformly. The preparation method of the supplement is to mix the raw materials uniformly.

[0077] Example 4

[0078] This embodiment discloses a high-speed copper etching solution for a TFT-LCD wet process, wherein the etching solution includes a main etching agent and a supplement;

[0079] The main etchant includes the following components by mass percentage: 12% hydrogen peroxide, 2.8% 3-diethylaminopropylamine, 1.2% malonic acid, 3.500% citric acid, 0.020% malic acid, 0.008% 5-aminotetrazole, 0.160% phenylurea, 0.150% nitric acid, and the balance is deionized water;

[0080] The supplement comprises the following components in percentage by mass: 17.500% of 3-diethylaminopropylamine, 12.000% of triisopropanolamine, 25.000% of citric acid, 1.250% of phenylurea, 0.080% of 5-aminotetrazole, 7.500% of malonic acid, and the balance is deionized water.

[0081] The preparation method of the main etchant is to mix the raw materials uniformly. The preparation method of the supplement is to mix the raw materials uniformly.

[0082] Example 5

[0083] This embodiment discloses a high-speed copper etching solution for a TFT-LCD wet process, wherein the etching solution includes a main etching agent and a supplement;

[0084] The main etchant includes the following components by mass percentage: 12.50% hydrogen peroxide, 3.30% 3-diethylaminopropylamine, 1.20% malonic acid, 3.00% citric acid, 0.05% malic acid, 0.008% 5-aminotetrazole, 0.08% phenylurea, 1.00% nitric acid, and the balance is deionized water;

[0085] The supplement includes the following components in percentage by mass: 10.00% of 3-diethylaminopropylamine, 5.000% of triisopropanolamine, 15.000% of citric acid, 0.500% of phenylurea, 0.010% of 5-aminotetrazole, 3.00% of malonic acid, and the balance is deionized water.

[0086] The preparation method of the main etchant is to mix the raw materials uniformly. The preparation method of the supplement is to mix the raw materials uniformly.

[0087] Example 6

[0088] This embodiment discloses a high-speed copper etching solution for a TFT-LCD wet process, wherein the etching solution includes a main etching agent and a supplement;

[0089] The main etchant includes the following components by mass percentage: 12.50% hydrogen peroxide, 3.30% 3-diethylaminopropylamine, 1.20% malonic acid, 3.00% citric acid, 0.05% malic acid, 0.008% 5-aminotetrazole, 0.08% phenylurea, 1.00% nitric acid, and the balance is deionized water;

[0090] The supplement includes the following components in percentage by mass: 25.00% of 3-diethylaminopropylamine, 19.000% of triisopropanolamine, 35.000% of citric acid, 2.00% of phenylurea, 0.20% of 5-aminotetrazole, 10.00% of malonic acid, and the balance is deionized water.

[0091] The preparation method of the main etchant is to mix the raw materials uniformly. The preparation method of the supplement is to mix the raw materials uniformly.

[0092] Example 7

[0093] This embodiment discloses a high-speed copper etching solution for a TFT-LCD wet process, wherein the etching solution includes a main etching agent and a supplement;

[0094] The main etchant includes the following components by mass percentage: 12.50% hydrogen peroxide, 3.30% 3-diethylaminopropylamine, 1.20% malonic acid, 3.00% citric acid, 0.05% malic acid, 0.008% 5-aminotetrazole, 0.08% phenylurea, 1.00% nitric acid, and the balance is deionized water;

[0095] The supplement comprises the following components in percentage by mass: 18.500% of 3-diethylaminopropylamine, 6.00% of triisopropanolamine, 20.20% of citric acid, 0.67% of phenylurea, 0.15% of 5-aminotetrazole, 8.30% of malonic acid, and the balance is deionized water.

[0096] The preparation method of the main etchant is to mix the raw materials uniformly. The preparation method of the supplement is to mix the raw materials uniformly.

[0097] Comparative Example 1

[0098] This comparative example discloses an etching solution, which includes a main etching agent and a supplement;

[0099] The main etchant includes the following components by mass percentage: 10% hydrogen peroxide, 3.5% 3-diethylaminopropylamine, 1.20% malonic acid, 3.00% citric acid, 0.05% malic acid, 0.008% 5-aminotetrazole, 0.08% phenylurea, 1.00% nitric acid, 0.005% ammonium fluoride, and the balance is deionized water;

[0100] The supplement includes the following components in percentage by mass: 14% of 3-diethylaminopropylamine, 27% of citric acid, 1.28% of phenylurea, 0.25% of 5-aminotetrazole, 0.40% of ammonium fluoride, and the balance is deionized water.

[0101] The preparation method of the main etchant is to mix the raw materials uniformly. The preparation method of the supplement is to mix the raw materials uniformly.

[0102] Comparative Example 2

[0103] This comparative example discloses an etching agent liquid, including an etching main agent and a supplement, the etching main agent includes the following components in mass percentage: 11.5% H2O2, 9% RS, 7.3% TIPA, 0.08% BJN, 0.038% DZ, 0.2% DLS, 0.1% BS2, and the balance is deionized water; the supplement includes the following components in mass percentage: 16% MEA, 3% IDA, 45% RS, 1% BS2, 1.28% BJN, 0.2% DZ, and the balance is deionized water.

[0104] Comparative Example 3

[0105] Compared with Example 1, this comparative example differs in the composition of the supplement, which is as follows:

[0106] The supplement includes the following components in percentage by mass: 14% of 3-diethylaminopropylamine, 9% of triisopropanolamine, 27% of citric acid, 1.28% of phenylurea, 0.25% of 5-aminotetrazole, 6.40% of malonic acid, 0.40% of ammonium fluoride, and the balance is deionized water.

[0107] Comparative Example 4

[0108] Compared with Example 1, this comparative example differs in the composition of the supplement, which is as follows:

[0109] The supplement includes the following components in percentage by mass: 16.8% of 3-diethylaminopropylamine, 4% of triisopropanolamine, 2% of malonic acid, 26% of citric acid, 1.28% of phenylurea, 0.08% of 5-aminotetrazole, and the balance is deionized water.

[0110] Comparative Example 5

[0111] Compared with Example 1, this comparative example differs in the composition of the supplement, which is as follows:

[0112] The supplement includes the following components in percentage by mass: 16.8% of 3-diethylaminopropylamine, 20% of triisopropanolamine, 26% of citric acid, 1.28% of phenylurea, 0.08% of 5-aminotetrazole, 11.00% of malonic acid, and the balance is deionized water.

[0113] Comparative Example 6

[0114] Compared with Example 1, this comparative example differs in the composition of the supplement, which is as follows:

[0115] The supplement includes the following components in percentage by mass: 16.8% of 3-diethylaminopropylamine, 26% of citric acid, 1.28% of phenylurea, 0.08% of 5-aminotetrazole, 6.40% of malonic acid, and the balance is deionized water.

[0116] Comparative Example 7

[0117] Compared with Example 1, this comparative example differs in the composition of the supplement, which is as follows:

[0118] The supplement includes the following components in percentage by mass: 16.8% of 3-diethylaminopropylamine, 9% of triisopropanolamine, 26% of citric acid, 1.28% of phenylurea, 0.08% of 5-aminotetrazole, and the balance is deionized water.

[0119] Comparative Example 8

[0120] Compared with Example 1, this comparative example differs in the composition of the supplement, which is as follows:

[0121] The supplement includes the following components in percentage by mass: 16.8% of 3-diethylaminopropylamine, 9% of triisopropanolamine, 26% of citric acid, 1.28% of phenylurea, 0.25% of 5-aminotetrazole, 6.40% of malonic acid, and the balance is deionized water.

[0122] Comparative Example 9

[0123] Compared with Example 1, this comparative example differs in the composition of the supplement, which is as follows:

[0124] The supplement includes the following components in percentage by mass: 14% of 3-diethylaminopropylamine, 27% of citric acid, 1.28% of phenylurea, 0.25% of 5-aminotetrazole, 0.40% of ammonium fluoride, and the balance is deionized water.

[0125] Comparative Example 10

[0126] This comparative example discloses a wet process high-speed copper etching solution, the etching solution comprising a main etching agent and a supplement;

[0127] The main etchant includes the following components by mass percentage: 12.50% hydrogen peroxide, 3.30% 3-diethylaminopropylamine, 1.20% malonic acid, 0.05% malic acid, 0.008% 5-aminotetrazole, 0.08% phenylurea, 1.00% nitric acid, and the balance is deionized water;

[0128] The supplement comprises the following components in percentage by mass: 9.000% of triisopropanolamine, 26.000% of citric acid, 1.28% of phenylurea, 0.08% of 5-aminotetrazole, 6.400% of malonic acid, and the balance is deionized water.

[0129] The preparation method of the main etchant is to mix the raw materials uniformly. The preparation method of the supplement is to mix the raw materials uniformly.

[0130] Comparative Example 11

[0131] This comparative example discloses a wet process high-speed copper etching solution, the etching solution comprising a main etching agent and a supplement;

[0132] The main etchant includes the following components by mass percentage: 12.50% hydrogen peroxide, 3.30% 3-diethylaminopropylamine, 1.20% malonic acid, 0.008% 5-aminotetrazole, 0.08% phenylurea, 1.00% nitric acid, and the balance is deionized water;

[0133] The supplement comprises the following components in percentage by mass: 25.80% of triisopropanolamine, 26.000% of citric acid, 1.28% of phenylurea, 0.08% of 5-aminotetrazole, 6.400% of malonic acid, and the balance is deionized water.

[0134] The preparation method of the main etchant is to mix the raw materials uniformly. The preparation method of the supplement is to mix the raw materials uniformly.

[0135] Comparative Example 12

[0136] This comparative example discloses a wet process high-speed copper etching solution, the etching solution comprising a main etching agent and a supplement;

[0137] The main etchant includes the following components by mass percentage: 12.50% hydrogen peroxide, 3.30% 3-diethylaminopropylamine, 3.00% citric acid, 0.008% 5-aminotetrazole, 0.08% phenylurea, 1.00% nitric acid, and the balance is deionized water;

[0138] The supplement includes the following components in percentage by mass: 16.80% of 3-diethylaminopropylamine, 9.00% of triisopropanolamine, 1.28% of phenylurea, 0.08% of 5-aminotetrazole, 32.40% of malonic acid, and the balance is deionized water.

[0139] The preparation method of the main etchant is to mix the raw materials uniformly. The preparation method of the supplement is to mix the raw materials uniformly.

[0140] Comparative Example 13

[0141] This comparative example discloses a wet process high-speed copper etching solution, the etching solution comprising a main etching agent and a supplement;

[0142] The main etchant includes the following components by mass percentage: 12.50% hydrogen peroxide, 3.30% 3-diethylaminopropylamine, 3.00% citric acid, 0.05% malic acid, 0.008% 5-aminotetrazole, 0.08% phenylurea, 1.00% nitric acid, and the balance is deionized water;

[0143] The supplement includes the following components in percentage by mass: 16.80% of 3-diethylaminopropylamine, 9.00% of triisopropanolamine, 26.0% of citric acid, 1.28% of phenylurea, 0.08% of 5-aminotetrazole, and the balance is deionized water.

[0144] The preparation method of the main etchant is to mix the raw materials uniformly. The preparation method of the supplement is to mix the raw materials uniformly.

[0145] The etching experiments of Examples 1-7 and Comparative Examples 1-13 are now carried out as shown in Table 1. The etching method is conventional and will not be elaborated in detail here. The etching results are shown in Table 1. The SEM images of the film layers obtained after etching are shown in Table 1. Figure 1-26 As shown; Example 1 in SD There is no residue after etching as shown in the figure Figure 27 As shown, Comparative Example 9 is in SD There is no residue after etching as shown in the figure Figure 28 shown.

[0146] Table 1

[0147]

[0148]

[0149] As shown in Table 1, when etching on different metal film layers, the etching times of the etching solutions obtained in Examples 1-7 were all shorter than those of Comparative Examples 1-13. Comparative Example 1 had a slightly slower etching rate and a service life of up to 8000 / 640 ppm. Compared with Example 1, Example 2 had a slightly slower etching rate. Compared with Example 1, Example 3 had a lower overall etching rate. Compared with Example 1, Example 4 had a lower overall etching rate. Compared with Example 1, Example 5 had a lower overall etching rate. Compared with Example 1, Example 6 had no significant difference in overall etching rate, CD Loss, or Taper, but the raw material cost accounted for a higher proportion. Compared with Example 1, Example 7 had a lower overall etching rate. However, the etching rates and etching effects obtained in Examples 2-7 were superior to those obtained in the comparative examples.

[0150] Comparative Example 2 has a slow etching rate, fails to meet the requirements of high-speed etching, and has a large etching angle; Comparative Example 3 has a large taper angle and has metal molybdenum residue; Comparative Example 4 has a slow etching rate and slight tailing; Comparative Example 5 has undercutting and a short solution life; Comparative Example 6 has a maximum copper dissolution of 8000ppm, but there are right angles and metal molybdenum residue; Comparative Examples 7 and 8 both have excessive pH, undercutting, and a short solution life; Comparative Example 9 has tailing, residue, and a maximum copper dissolution of 7500ppm; Comparative Example 10 has an excessively fast etching rate, increased CDLoss, and residue; Comparative Example 11 has a slow etching rate, reduced CDLoss, and undercut; Comparative Examples 12 and 13 both have reduced CDLoss. The etching angles of the etching solutions obtained in Examples 1-7 are relatively reasonable and there is no residue, indicating that the etching solutions obtained in Examples 1-7 have the advantages of faster etching speed, uniform and stable etching angles Taper and CDloss, no undercutting, drilling, metal residue, etc., high copper dissolution, and long service life.

[0151] The above description is only a preferred embodiment of the present application and is not intended to limit the present application. Any modifications, equivalent replacements and improvements made within the spirit and principles of the present application should be included in the scope of protection of the present application.

Claims

1. A TFT-LCD wet process high-speed copper etching solution, characterized in that: The copper etching solution includes a main etching agent and a supplement; The main etchant comprises the following components by mass percentage: 10% to 15% hydrogen peroxide, 2.8% to 3.8% of a first organic base, 2.71% to 5.9% of a first organic acid, 0.001% to 0.01% of a corrosion inhibitor, 0.01% to 0.2% of a hydrogen peroxide stabilizer, 0.1% to 2% of a pH regulator, and the balance being deionized water; The supplement comprises the following components in percentage by mass: 15% to 44% of a second organic base, 15% to 35% of a second organic acid, 0.5% to 2% of a hydrogen peroxide stabilizer, 0.01% to 0.2% of a corrosion inhibitor, 3% to 10% of a third organic acid, and the balance being deionized water.

2. The TFT-LCD wet process high-speed copper etching solution according to claim 1, characterized in that: The first organic acid includes at least one of malonic acid, citric acid and malic acid; preferably, the first organic acid includes malonic acid, citric acid and malic acid, the mass percentage of malonic acid in the main etchant is 0.7% to 1.7%, the mass percentage of citric acid is 2% to 4%, and the mass percentage of malic acid is 0.01% to 0.2%.

3. The TFT-LCD wet process high-speed copper etching solution according to claim 1, characterized in that: The second organic base includes 3-diethylaminopropylamine and / or triisopropanolamine; preferably, the second organic base includes 3-diethylaminopropylamine and triisopropanolamine, the mass percentage of 3-diethylaminopropylamine in the supplement is 10% to 25%, and the mass percentage of triisopropanolamine is 5% to 19%.

4. The TFT-LCD wet process high-speed copper etching solution according to claim 1, characterized in that: The first organic base is 3-diethylaminopropylamine; the corrosion inhibitor is 5-aminotetrazole; the hydrogen peroxide stabilizer is phenylurea; and the pH regulator is nitric acid.

5. The TFT-LCD wet process high-speed copper etching solution according to claim 1, characterized in that: The second organic acid is citric acid; and the third organic acid is malonic acid.

6. The TFT-LCD wet process high-speed copper etching solution according to claim 1, characterized in that: The main etchant comprises the following components by mass percentage: 10% to 15% hydrogen peroxide, 2.8% to 3.8% 3-diethylaminopropylamine, 0.7% to 1.7% malonic acid, 2% to 4% citric acid, 0.01% to 0.2% malic acid, 0.001% to 0.01% 5-aminotetrazole, 0.01% to 0.2% phenylurea, 0.1% to 2% nitric acid, and the balance is deionized water; The supplement comprises the following components in percentage by mass: 10% to 25% of 3-diethylaminopropylamine, 5% to 19% of triisopropanolamine, 15% to 35% of citric acid, 0.5% to 2% of phenylurea, 0.01% to 0.2% of 5-aminotetrazole, 3% to 10% of malonic acid, and the balance is deionized water.

7. The TFT-LCD wet process high-speed copper etching solution according to claim 8, characterized in that: The main etchant includes the following components by mass percentage: 12.50% hydrogen peroxide, 3.3% 3-diethylaminopropylamine, 1.2% malonic acid, 3.00% citric acid, 0.05% malic acid, 0.008% 5-aminotetrazole, 0.08% phenylurea, 1.00% nitric acid, and the balance is deionized water; The supplement comprises the following components by mass percentage: 16.80% of 3-diethylaminopropylamine, 9% of triisopropanolamine, 26% of citric acid, 1.28% of phenylurea, 0.08% of 5-aminotetrazole, 6.4% of malonic acid, and the balance is deionized water.

8. A method for etching a film layer containing copper, characterized in that: Etching is performed by contacting the copper etching solution according to any one of claims 1 to 7 with an etching object; preferably, during the etching process, for every 1000 ppm increase in the copper ion concentration in the copper etching solution, a supplement accounting for 0.1 to 13.4 wt % of the main etching agent is added.

9. Use of the etching solution according to any one of claims 1 to 7 for etching a liquid crystal panel comprising an oxide liquid crystal panel and a copper / molybdenum multilayer thin film.

10. The use according to claim 9, characterized in that The copper / molybdenum multilayer film includes a Cu / MoNbGate multilayer and / or a Cu / MoNb SD multilayer; preferably, the Cu / MoNb Gate multilayer includes and At least one of; preferably, the Cu / MoNb SD multi-film layer includes and / or

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