Tft-lcd wet process high-speed copper etching solution and application thereof

Abstract

The application relates to the field of etching liquid, and discloses a TFT-LCD wet process high-speed copper etching liquid and application thereof, the etching liquid comprises a main etchant and a supplement; the main etchant comprises 10-15 wt% hydrogen peroxide, 2.8-3.8 wt% a first organic alkali, 2.71-5.9 wt% a first organic acid, 0.001-0.01 wt% a corrosion inhibitor, 0.01-0.2 wt% a hydrogen peroxide stabilizer, 0.1-2 wt% a pH regulator, and the balance is deionized water; the supplement comprises 15-44 wt% a second organic alkali, 15-35 wt% a second organic acid, 0.5-2 wt% a hydrogen peroxide stabilizer, 0.01-0.2 wt% a corrosion inhibitor, 3-10 wt% a third organic acid, and the balance is deionized water. The etching liquid is environment-friendly and pollution-free, has a high etching speed, uniform and stable etching angle, no undercut, no drilling, no metal residue and the like, and a high copper dissolving amount.

Description

Technical Field

[0001] This application belongs to the field of copper etching solution technology for liquid crystal panels, and particularly relates to a high-speed copper etching solution for wet TFT-LCD processes and its application. Background Technology

[0002] The microcircuits of thin-film transistor liquid crystal displays (TFT-LCDs) are formed through a series of exposure and development processes. Specifically, photoresist (PR) is uniformly coated onto a substrate consisting of a metal film, a semiconductor film, and an insulating film. After illumination and development, a patterned photoresist is formed. Dry or wet etching is then used to remove the areas not covered by the photoresist. Finally, the PR is peeled off to form a patterned film layer. This process is repeated to form the microcircuit. In the field of TFT-LCD panels, there are two main metallization processes: aluminum and copper. Compared to the aluminum process, the core of the copper process is replacing the aluminum metal traces for the gate and source / drain electrodes in the TFT array substrate with copper. Copper has higher conductivity and lower resistivity, which can significantly reduce signal delay and is beneficial for the development of TFT-LCD panels towards larger sizes, higher resolutions, higher refresh rates, and higher transmittance. Considering the poor adhesion between copper and glass substrates, which could lead to Cu film detachment or damage during subsequent processes, 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 as buffer metals.

[0003] To effectively etch such multi-layered metal films, hydrogen peroxide-based copper etching solutions are widely used in the industry. A high-performance etching solution should possess suitable bond size loss (CD Loss), a large etching coefficient, minimal lateral etching, stable etching performance, excellent copper dissolution capacity, and easy-to-treat copper etching waste. However, in existing technologies, fluorine-containing etching solutions are commonly used to improve the etching effect on molybdenum. However, fluorine-containing etching solutions increase the difficulty and cost of treating copper etching waste, causing environmental pollution. Furthermore, existing etching solutions are prone to producing unsuitable angle tapers, resulting in poor etching. An excessively large angle can lead to breakage during the deposition of the next metal layer, causing metal wire breaks and affecting product performance; an excessively small angle causes thermal expansion and contraction deformation, affecting the direction and precision of metal wiring. Additionally, although some hydrogen peroxide-based copper etching solutions in existing technologies can achieve a service life of 8000-10000 ppm, their etching rate is too slow, and the etching process is unstable, resulting in poor CD Loss uniformity, as well as the appearance of chamfers and cracks. Summary of the Invention

[0004] In view of the shortcomings of the prior art, the present invention provides a high-speed copper etching solution for wet process of TFT-LCD and its application. The etching solution has the advantages of fast etching rate, stable etching reaction, good etching effect and long service life.

[0005] To achieve the above-mentioned objectives, the technical solution adopted in this application is as follows:

[0006] In a first aspect, this application provides a high-speed copper etching solution for wet TFT-LCD processes, the copper etching solution comprising a main etchant and a supplementary agent;

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

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

[0009] As one possible design, the first organic acid includes malonic acid, citric acid, and malic acid; the main etchant contains 0.7% to 1.7% malonic acid by mass, 2% to 4% citric acid by mass, and 0.01% to 0.2% malic acid by mass.

[0010] As one possible design, the second organic base comprises 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 one possible design, the first organic base is 3-diethylaminopropylamine; the corrosion inhibitor is 5-aminotetrazolium; the hydrogen peroxide stabilizer is phenylurea; and the pH adjuster is nitric acid.

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

[0013] As one possible design, the main etchant comprises, by mass percentage: 10%–15% hydrogen peroxide, 2.8%–3.8% 3-diethylaminopropylamine, 0.7%–1.7% malonic acid, 2%–4% citric acid, 0.01%–0.2% malic acid, 0.001%–0.01% 5-aminotetrazole, 0.01%–0.2% phenylurea, 0.1%–2% nitric acid, with the balance being deionized water;

[0014] The supplement comprises, by mass percentage: 10%–25% 3-diethylaminopropylamine, 5%–19% triisopropanolamine, 15%–35% citric acid, 0.5%–2% phenylurea, 0.01%–0.2% 5-aminotetrazolium, 3%–10% malonic acid, with the balance being deionized water.

[0015] As one possible design, the main etchant comprises, 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-aminotetrazolium, 0.08% phenylurea, 1.00% nitric acid, with the balance being deionized water;

[0016] The supplement comprises, by weight percentage: 16.80% 3-diethylaminopropylamine, 9% triisopropanolamine, 26% citric acid, 1.28% phenylurea, 0.08% 5-aminotetrazolium, 6.4% malonic acid, with the balance being deionized water.

[0017] Secondly, the present invention provides an etching method for a copper-containing film layer, wherein etching is performed by contacting the aforementioned 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, a supplementary agent is added at a ratio of 0.1 to 13.4 wt% of the main etchant. In practical application, the higher the copper ion concentration, the higher the proportion of supplementary agent added.

[0018] Thirdly, the present invention provides an application of the aforementioned etching solution in etching a liquid crystal panel having an oxide liquid crystal panel and a copper / molybdenum-based multilayer film.

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

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

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

[0022] 2. Capable of simultaneously supporting multiple substrates: such as Cu / MoNb Gate multi-layer thickness (GT) GT GT and GT ) and Cu / MoNb SD multilayer thickness (SD and SD ).

[0023] 3. Fast etching speed, uniform and stable etching angle TaperCD loss, no undercutting, drilling, metal residue, etc., and high copper dissolution capacity, resulting in a long service life. Attached Figure Description

[0024] To more clearly illustrate the technical solutions in the embodiments of this application, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0025] Figure 1 The etching solution provided in Embodiment 1 of this application is used in SD Etching angle diagram showing the highest copper dissolution on the film layer at 11,000 ppm;

[0026] Figure 2 The etching solution provided in Example 1 of this application is used in GT Etching angle diagram showing the highest copper dissolution on the film layer at 11,000 ppm;

[0027] Figure 3 The etching solution provided in Example 1 of this application is used in GT Etching angle diagram showing the highest copper dissolution on the film layer at 11,000 ppm;

[0028] Figure 4 The etching solution provided in Example 1 of this application is used in GT Etching angle diagram showing the highest copper dissolution on the film layer at 11,000 ppm;

[0029] Figure 5 The etching solution provided in Embodiment 1 of this application is used in SD Etching angle diagram showing the highest copper dissolution on the film layer at 11,000 ppm;

[0030] Figure 6 The etching solution provided in Example 1 of this application is used in GT Etching angle diagram showing the highest copper dissolution on the film layer at 11,000 ppm;

[0031] Figure 7 The etching solution provided in Embodiment 2 of this application is used in SD Etching angle diagram showing the highest copper dissolution on the film layer at 11,000 ppm;

[0032] Figure 8 The etching solution provided in Embodiment 3 of this application is used in SD Etching angle diagram showing the highest copper dissolution on the film layer at 11,000 ppm;

[0033] Figure 9 The etching solution provided in Example 4 of this application is used in GT Etching angle diagram showing the highest copper dissolution on the film layer at 11,000 ppm;

[0034] Figure 10 The etching solution provided in Example 5 of this application is used in GT Etching angle diagram showing the highest copper dissolution on the film layer at 11,000 ppm;

[0035] Figure 11 The etching solution provided in Embodiment 6 of this application is used in GT Etching angle diagram showing the highest copper dissolution on the film layer at 11,000 ppm;

[0036] Figure 12 The etching solution provided in Embodiment 7 of this application is used in SD Etching angle diagram showing the highest copper dissolution on the film layer at 11,000 ppm;

[0037] Figure 13 The etching solution provided in Comparative Example 1 of this application is used in SD Etching angle diagram showing the highest copper dissolution on the film layer at 8000ppm;

[0038] Figure 14 The etching solution provided in Comparative Example 1 of this application is used in GT Etching angle diagram showing the highest copper dissolution on the film layer at 8000ppm;

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

[0040] Figure 16 The etching solution provided in Comparative Example 3 of this application is used in GT Etching angle diagram showing the highest copper dissolution on the film layer at 8000ppm;

[0041] Figure 17 The etching solution provided in Comparative Example 4 of this application is used in GT Etching angle diagram showing the highest copper dissolution on the film layer at 8000ppm;

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

[0043] Figure 19 The etching solution provided in Comparative Example 6 of this application is used in GT Etching angle diagram showing the highest copper dissolution on the film layer at 8000ppm;

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

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

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

[0047] Figure 23 This is an etching angle diagram showing the highest copper dissolution of 8000ppm on the GT 6500 / / 150A film layer provided by the etching solution in Comparative Example 10 of this application;

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

[0049] Figure 25 The etching solution provided in Comparative Example 12 of this application is used in GT Etching angle diagram showing the highest copper dissolution on the film layer at 8000ppm;

[0050] Figure 26 The etching solution provided in Comparative Example 13 of this application is used in GT Etching angle diagram showing the highest copper dissolution on the film layer at 8000ppm;

[0051] Figure 27 The etching solution provided in Embodiment 1 of this application is used in SD Image showing the surface condition of the film after etching, where the highest copper dissolution on the film is 11,000 ppm;

[0052] Figure 28 The etching solution provided in Comparative Example 9 of this application is used in SD Image showing the surface condition of the film after etching, where the highest copper dissolution on the film is 7500ppm. Detailed Implementation

[0053] To make the technical problems, technical solutions, and beneficial effects of this application clearer, the following detailed description is provided in conjunction with embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the scope of this application.

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

[0055] It should be understood that in the various embodiments of this application, the order of the above processes does not imply the order of execution. Some or all steps may 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 this application.

[0056] The terminology used in the embodiments of this application is for the purpose of describing particular embodiments only and is not intended to be limiting of this application. The singular forms “a,” “the,” and “the” used in the embodiments of this application and the appended claims are also intended to include the plural forms unless the context clearly indicates otherwise.

[0057] The weights of the relevant components mentioned in the embodiments of this application can refer not only to the specific content of each component, but also to the proportional relationship between the weights of the components. Therefore, any scaling up or down of the content of the relevant components according to the embodiments of this application is within the scope disclosed in the embodiments of this application. Specifically, the mass described in the embodiments of this application can be a mass unit known in the chemical industry, such as μg, mg, g, or kg.

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

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

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

[0061] The copper concentrations are as follows: 1000 ppm, 0.6 wt% supplement; 2000 ppm, 1.8 wt% supplement; 3000 ppm, 3 wt% supplement; 4000 ppm, 4.2 wt% supplement; 5000 ppm, 5.4 wt% supplement; 6000 ppm, 6.6 wt% supplement; 7000 ppm, 8.3 wt% supplement; 8000 ppm, 10 wt% supplement; 9000 ppm, 11.2 wt% supplement; 10000 ppm, 13.4 wt% supplement.

[0062] Example 1

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

[0064] The main etchant comprises, 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-aminotetrazolium, 0.08% phenylurea, 1.00% nitric acid, with the balance being deionized water;

[0065] The supplement contains the following ingredients by mass percentage: 16.80% 3-diethylaminopropylamine, 9% triisopropanolamine, 26% citric acid, 1.28% phenylurea, 0.08% 5-aminotetrazolium, 6.4% malonic acid, with the balance being deionized water.

[0066] The main etchant is prepared by mixing all raw materials evenly. The supplement is prepared by mixing all raw materials evenly.

[0067] Example 2

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

[0069] The main etchant comprises, 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, with the balance being deionized water.

[0070] The supplement contains the following ingredients by mass percentage: 10% 3-diethylaminopropylamine, 5% triisopropanolamine, 15% citric acid, 0.500% phenylurea, 0.010% 5-aminotetrazolium, 3% malonic acid, with the balance being deionized water.

[0071] The main etchant is prepared by mixing all raw materials evenly. The supplement is prepared by mixing all raw materials evenly.

[0072] Example 3

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

[0074] The main etchant comprises, 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, with the balance being deionized water.

[0075] The supplement contains the following ingredients by mass percentage: 25.000% 3-diethylaminopropylamine, 19.000% triisopropanolamine, 35.000% citric acid, 2.000% phenylurea, 0.200% 5-aminotetrazole, 10.000% malonic acid, with the balance being deionized water.

[0076] The main etchant is prepared by mixing all raw materials evenly. The supplement is prepared by mixing all raw materials evenly.

[0077] Example 4

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

[0079] The main etchant comprises, 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-aminotetrazolium, 0.160% phenylurea, 0.150% nitric acid, with the balance being deionized water.

[0080] The supplement contains the following ingredients by mass percentage: 17.500% 3-diethylaminopropylamine, 12.000% triisopropanolamine, 25.000% citric acid, 1.250% phenylurea, 0.080% 5-aminotetrazole, 7.500% malonic acid, with the balance being deionized water.

[0081] The main etchant is prepared by mixing all raw materials evenly. The supplement is prepared by mixing all raw materials evenly.

[0082] Example 5

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

[0084] The main etchant comprises, 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, with the balance being deionized water.

[0085] The supplement contains the following ingredients by mass percentage: 10.00% 3-diethylaminopropylamine, 5.000% triisopropanolamine, 15.000% citric acid, 0.500% phenylurea, 0.010% 5-aminotetrazole, 3.00% malonic acid, with the balance being deionized water.

[0086] The main etchant is prepared by mixing all raw materials evenly. The supplement is prepared by mixing all raw materials evenly.

[0087] Example 6

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

[0089] The main etchant comprises, 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, with the balance being deionized water.

[0090] The supplement contains the following ingredients by mass percentage: 25.00% 3-diethylaminopropylamine, 19.000% triisopropanolamine, 35.000% citric acid, 2.00% phenylurea, 0.20% 5-aminotetrazole, 10.00% malonic acid, with the balance being deionized water.

[0091] The main etchant is prepared by mixing all raw materials evenly. The supplement is prepared by mixing all raw materials evenly.

[0092] Example 7

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

[0094] The main etchant comprises, 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, with the balance being deionized water.

[0095] The supplement contains the following ingredients by mass percentage: 18.500% 3-diethylaminopropylamine, 6.00% triisopropanolamine, 20.20% citric acid, 0.67% phenylurea, 0.15% 5-aminotetrazolium, 8.30% malonic acid, with the balance being deionized water.

[0096] The main etchant is prepared by mixing all raw materials evenly. The supplement is prepared by mixing all raw materials evenly.

[0097] Comparative Example 1

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

[0099] The main etchant comprises, 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-aminotetrazolium, 0.08% phenylurea, 1.00% nitric acid, 0.005% ammonium fluoride, with the balance being deionized water.

[0100] The supplement contains the following ingredients by mass percentage: 14% 3-diethylaminopropylamine, 27% citric acid, 1.28% phenylurea, 0.25% 5-aminotetrazolium, 0.40% ammonium fluoride, with the balance being deionized water.

[0101] The main etchant is prepared by mixing all raw materials evenly. The supplement is prepared by mixing all raw materials evenly.

[0102] Comparative Example 2

[0103] This comparative example discloses an etching solution comprising an etching main agent and a supplementary agent. The etching main agent comprises the following components by mass percentage: 11.5% H2O2, 9% RS, 7.3% TIPA, 0.08% BJN, 0.038% DZ, 0.2% DLS, 0.1% BS2, with the balance being deionized water. The supplementary agent comprises the following components by mass percentage: 16% MEA, 3% IDA, 45% RS, 1% BS2, 1.28% BJN, 0.2% DZ, with the balance being deionized water.

[0104] Comparative Example 3

[0105] The difference between this comparative example and Example 1 lies in the composition of the supplement, as detailed below:

[0106] The supplement contains the following ingredients by mass percentage: 14% 3-diethylaminopropylamine, 9% triisopropanolamine, 27% citric acid, 1.28% phenylurea, 0.25% 5-aminotetrazolium, 6.40% malonic acid, 0.40% ammonium fluoride, with the balance being deionized water.

[0107] Comparative Example 4

[0108] The difference between this comparative example and Example 1 lies in the composition of the supplement, as detailed below:

[0109] The supplement contains the following ingredients by weight percentage: 16.8% 3-diethylaminopropylamine, 4% triisopropanolamine, 2% malonic acid, 26% citric acid, 1.28% phenylurea, 0.08% 5-aminotetrazolium, with the balance being deionized water.

[0110] Comparative Example 5

[0111] The difference between this comparative example and Example 1 lies in the composition of the supplement, as detailed below:

[0112] The supplement contains the following ingredients by mass percentage: 16.8% 3-diethylaminopropylamine, 20% triisopropanolamine, 26% citric acid, 1.28% phenylurea, 0.08% 5-aminotetrazolium, 11.00% malonic acid, with the balance being deionized water.

[0113] Comparative Example 6

[0114] The difference between this comparative example and Example 1 lies in the composition of the supplement, as detailed below:

[0115] The supplement contains the following ingredients by mass percentage: 16.8% 3-diethylaminopropylamine, 26% citric acid, 1.28% phenylurea, 0.08% 5-aminotetrazolium, 6.40% malonic acid, and the balance being deionized water.

[0116] Comparative Example 7

[0117] The difference between this comparative example and Example 1 lies in the composition of the supplement, as detailed below:

[0118] The supplement contains the following ingredients by weight percentage: 16.8% 3-diethylaminopropylamine, 9% triisopropanolamine, 26% citric acid, 1.28% phenylurea, 0.08% 5-aminotetrazolium, with the balance being deionized water.

[0119] Comparative Example 8

[0120] The difference between this comparative example and Example 1 lies in the composition of the supplement, as detailed below:

[0121] The supplement contains the following ingredients by mass percentage: 16.8% 3-diethylaminopropylamine, 9% triisopropanolamine, 26% citric acid, 1.28% phenylurea, 0.25% 5-aminotetrazolium, 6.40% malonic acid, and the balance being deionized water.

[0122] Comparative Example 9

[0123] The difference between this comparative example and Example 1 lies in the composition of the supplement, as detailed below:

[0124] The supplement contains the following ingredients by mass percentage: 14% 3-diethylaminopropylamine, 27% citric acid, 1.28% phenylurea, 0.25% 5-aminotetrazolium, 0.40% ammonium fluoride, with the balance being deionized water.

[0125] Comparative Example 10

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

[0127] The main etchant comprises, by mass percentage: 12.50% hydrogen peroxide, 3.30% 3-diethylaminopropylamine, 1.20% malonic acid, 0.05% malic acid, 0.008% 5-aminotetrazolium, 0.08% phenylurea, 1.00% nitric acid, with the balance being deionized water;

[0128] The supplement contains, by weight percentage: 9.000% triisopropanolamine, 26.000% citric acid, 1.28% phenylurea, 0.08% 5-aminotetrazole, 6.400% malonic acid, with the balance being deionized water.

[0129] The main etchant is prepared by mixing all raw materials evenly. The supplement is prepared by mixing all raw materials evenly.

[0130] Comparative Example 11

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

[0132] The main etchant comprises, 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, with the balance being deionized water.

[0133] The supplement contains, by weight percentage: 25.80% triisopropanolamine, 26.000% citric acid, 1.28% phenylurea, 0.08% 5-aminotetrazole, 6.400% malonic acid, with the balance being deionized water.

[0134] The main etchant is prepared by mixing all raw materials evenly. The supplement is prepared by mixing all raw materials evenly.

[0135] Comparative Example 12

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

[0137] The main etchant comprises, 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, with the balance being deionized water.

[0138] The supplement contains the following ingredients by mass percentage: 16.80% 3-diethylaminopropylamine, 9.00% triisopropanolamine, 1.28% phenylurea, 0.08% 5-aminotetrazolium, 32.40% malonic acid, with the balance being deionized water.

[0139] The main etchant is prepared by mixing all raw materials evenly. The supplement is prepared by mixing all raw materials evenly.

[0140] Comparative Example 13

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

[0142] The main etchant comprises, by mass percentage: 12.50% hydrogen peroxide, 3.30% 3-diethylaminopropylamine, 3.00% citric acid, 0.05% malic acid, 0.008% 5-aminotetrazolium, 0.08% phenylurea, 1.00% nitric acid, with the balance being deionized water.

[0143] The supplement contains the following ingredients by mass percentage: 16.80% 3-diethylaminopropylamine, 9.00% triisopropanolamine, 26.0% citric acid, 1.28% phenylurea, 0.08% 5-aminotetrazolium, with the balance being deionized water.

[0144] The main etchant is prepared by mixing all raw materials evenly. The supplement is prepared by mixing all raw materials evenly.

[0145] Etching experiments were conducted on Examples 1-7 and Comparative Examples 1-13 as shown in Table 1. The etching method used was existing and will not be described in detail here. The etching results are shown in Table 1, and the SEM images of the films obtained after etching are shown below. Figure 1-26 As shown; Example 1 in SD The image shows the result of no residue after etching. Figure 27 As shown, Comparative Example 9 in SD The image shows the result of no residue after etching. Figure 28 As shown.

[0146] Table 1

[0147]

[0148]

[0149] As shown in Table 1, when etching on different metal film layers, the etching time of the etching solutions obtained in Examples 1-7 is shorter than that of Comparative Examples 1-13. Comparative Example 1 has a slightly slower etching rate and the highest service life of 8000 / 640ppm. Compared with Example 1, Example 2 has a slightly slower etching rate. Compared with Example 1, Example 3 has a lower overall etching rate. Compared with Example 1, Example 4 has a lower overall etching rate. Compared with Example 1, Example 5 has a lower overall etching rate. Compared with Example 1, Example 6 has no significant difference in overall etching rate, CD Loss, and Taper, but the raw material cost accounts for a larger proportion. Compared with Example 1, Example 7 has a lower overall etching rate. However, the etching rate and etching effect of Examples 2-7 are better than those of the comparative examples.

[0150] Comparative Example 2 exhibits a slow etching rate, failing to meet high-speed etching requirements, and has a relatively large etching angle. Comparative Example 3 has a relatively large Taper angle, resulting in molybdenum residue. Comparative Example 4 shows a slow etching rate with slight tailing. Comparative Example 5 shows undercutting and a short solution life. Comparative Example 6 has a maximum copper dissolution of 8000 ppm, but exhibits right angles and molybdenum residue. Comparative Examples 7 and 8 both have excessively high pH, ​​undercutting, and short solution life. Comparative Example 9 shows tailing and residue, with a maximum copper dissolution of 7500 ppm. Comparative Example 10 has an excessively fast etching rate, increased CDLoss, and residue. Comparative Example 11 has a slow etching rate, decreased CDLoss, and undercutting. Comparative Examples 12 and 13 both show decreased CDLoss. The etching solutions obtained in Examples 1-7 have reasonable etching angles and no residue, indicating that the etching solutions obtained in Examples 1-7 have advantages such as faster etching speed, uniform and stable etching angle Taper and CDLoss, no undercutting, drilling, or metal residue, high copper dissolution, and long service life.

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

Claims

1. A high-speed copper etching solution for TFT-LCD wet process, characterized in that, The copper etching solution comprises a main etchant and a supplement; The main etchant comprises, by mass percentage, 10-15% of hydrogen peroxide, 2.8-3.8% of a first organic base, 2.71-5.9% of a first organic acid, 0.001-0.01% of a corrosion inhibitor, 0.01-0.2% of a hydrogen peroxide stabilizer, 0.1-2% of a pH regulator, and the balance of deionized water; The supplement comprises, by mass percentage, 15-44% of a second organic base, 15-35% of a second organic acid, 0.5-2% of a hydrogen peroxide stabilizer, 0.01-0.2% of a corrosion inhibitor, 3-10% of a third organic acid, and the balance of deionized water; The first organic acid comprises malonic acid, citric acid, and malic acid, the mass percentage of malonic acid in the main etchant is 0.7-1.7%, the mass percentage of citric acid is 2-4%, and the mass percentage of malic acid is 0.01-0.2%; The second organic base comprises 3-diethylaminopropylamine and triisopropanolamine, the mass percentage of 3-diethylaminopropylamine in the supplement is 10-25%, and the mass percentage of triisopropanolamine is 5-19%; The first organic base is 3-diethylaminopropylamine, the corrosion inhibitor is 5-amino tetrazole, the hydrogen peroxide stabilizer is phenylurea, and the pH regulator is nitric acid; The second organic acid is citric acid, and the third organic acid is malonic acid.

2. The high-speed copper etching solution for TFT-LCD wet process according to claim 1, characterized in that, The main etchant comprises, by mass percentage, 12.50% of hydrogen peroxide, 3.3% of 3-diethylaminopropylamine, 1.2% of malonic acid, 3.00% of citric acid, 0.05% of malic acid, 0.008% of 5-amino tetrazole, 0.08% of phenylurea, 1.00% of nitric acid, and the balance of deionized water; The supplement comprises, by mass percentage, 16.80% of 3-diethylaminopropylamine, 9% of triisopropanolamine, 26% of citric acid, 1.28% of phenylurea, 0.08% of 5-amino tetrazole, 6.4% of malonic acid, and the balance of deionized water.

3. An etching method of a film layer containing copper, characterized by, The copper etching solution as claimed in any one of claims 1-2 is used to contact an etching object, so as to perform etching.

4. The etching method according to claim 3, characterized by, In the etching process, for every 1000 ppm increase in the copper ion concentration per liter of the copper etching solution, 0.1-13.4 wt% of the supplement based on the main etchant is added.

5. The etching solution as claimed in any one of claims 1-2 is used to etch a liquid crystal panel provided with an oxide liquid crystal panel and a copper / molybdenum multilayer film.

6. Use according to claim 5, characterized in that, The copper / molybdenum multilayer film comprises a Cu / MoNb Gate multi-film layer and / or a Cu / MoNb SD multi-film layer.

7. Use according to claim 6, characterized in that, The Cu / MoNb Gate multi-film layer comprises at least one of GT 3500 / 150 Å, GT 3500 / 350 Å, GT 6500 / 150 Å, and GT 6500 / 350 Å; and the Cu / MoNb SD multi-film layer comprises SD3000 / 350 Å and / or SD 6500 / 350 Å.

Images