Developing solution for manufacturing AMOLED panel and preparation method thereof

Abstract

The invention discloses a developing solution for manufacturing an AMOLED (Active Matrix / Organic Light Emitting Diode) panel and a preparation method of the developing solution. The invention discloses a water-based metal cleaning agent which comprises the following components in percentage by weight: 2-5% of tetramethylammonium hydroxide, 0.5-5% of a composite metal protective agent consisting of at least two of 5-aminotetrazole, 2-mercaptobenzothiazole and 1-aminobenzotriazole, 0.5-3% of an organic carboxylate synergist, 1-5% of an organic solvent, 0.01-1% of a surfactant, 0.05-0.5% of a pH stabilizer, 0.001-0.1% of a metal chelating agent and the balance of ultrapure water. A preparation method of the water-based metal cleaning agent comprises the following steps: sequentially dissolving the components in a clean environment; and carrying out two-stage filtration, deoxidation (dissolved oxygen is less than or equal to 20ppb) and nitrogen-filled sealing to obtain a product with ultrahigh cleanliness (granularity is less than or equal to 25 pieces / mL). The corrosion rates of the developing solution to aluminum, silver and titanium are lower than 4 nm / min, 3.5 nm / min and 1 nm / min respectively, the performance is stable after the developing solution is stored for 30 days, the problems of multi-metal corrosion, developing residues and uniformity can be synchronously solved, and the manufacturing yield of AMOLED panels is remarkably improved.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of AMOLED panel manufacturing, and particularly relates to a developing solution for AMOLED panel manufacturing and a preparation method thereof. BACKGROUND

[0002] AMOLED (active-matrix organic light-emitting diode) panel manufacturing is a highly precise process, in which the photoetching technology is a key step for forming a fine circuit pattern. In this process, the developing solution as a key wet electronic chemical directly determines the quality of the photoresist pattern, and further affects the yield of the final product.

[0003] At present, the most widely used developing solution in the industry is a 2.38% tetramethylammonium hydroxide (TMAH) aqueous solution. This type of developing solution has occupied a dominant position in the field of microelectronic processing due to its extremely low metal ion content, which can effectively avoid metal ion pollution. However, with the development of AMOLED technology towards higher resolution and more complex structure, the Ti / Al / Ti composite metal layer commonly used in the array circuit and the silver material used in the electrode have put forward more stringent requirements for the developing solution. The traditional TMAH developing solution gradually exposes the following technical defects that need to be solved urgently when applied to AMOLED manufacturing: First, in terms of metal corrosion prevention, there are multiple metals with different properties such as Ag, Al, and Ti in the AMOLED array, and the existing single corrosion inhibitor (such as the commonly used benzotriazole) or arbitrary compounding scheme cannot effectively and evenly protect these three metals. Moreover, there is often an antagonistic effect between different corrosion inhibitor molecules, which cannot form a synergistically effective protection system. Second, the long-term storage stability of the developing solution as an alkaline system is a big problem. The introduction of trace metal impurities can catalyze the decomposition of effective components and may damage the passivation film formed by the corrosion inhibitor. At the same time, the presence of dissolved oxygen can accelerate the corrosion of sensitive metals such as silver. The conventional formula lacks a targeted solution to this problem. In addition, the existing developing solution preparation process cannot simultaneously ensure the ultra-high cleanliness and chemical stability of the solution. The conventional filtration and packaging methods cannot meet the stringent requirements of defect control for high-end AMOLED processes.

[0004] Therefore, the development of a new type of developing solution that can simultaneously and efficiently inhibit the corrosion of Ag, Al, and Ti, completely eliminate developing residues, and ensure excellent developing uniformity, while also having excellent long-term storage stability and cleanliness levels beyond existing standards, has become an urgent technical requirement in the field of AMOLED panel manufacturing. SUMMARY

[0005] The application aims to overcome the deficiencies of the prior art, and provides a developing solution for AMOLED panel manufacturing and a preparation method thereof. A preparation method of a developing solution for AMOLED panel manufacturing comprises the following steps: (1) In a clean environment, 40-60% of the total mass of the developing solution is added to a reaction kettle in the form of ultrapure water, and stirring is performed at a speed of 400-450 rpm at room temperature; (2) 2-5% of the total mass of the developing solution is slowly added in the form of an organic base, and stirring is continuously performed for 5 minutes until complete dissolution, wherein the organic base is a quaternary ammonium base organic compound, and specifically tetramethylammonium hydroxide; (3) 1-5% of the total mass of the developing solution is added in the form of an organic solvent, and stirring is performed until complete dissolution, wherein the organic solvent is at least one selected from the group consisting of dipropylene glycol methyl ether, ethylene glycol and N-methyl-2-pyrrolidone; (4) 0.5-5% of the total mass of the developing solution is added in the form of a metal protective agent, and stirring is performed until complete dissolution, wherein the metal protective agent is composed of at least two selected from the group consisting of 5-amino tetrazole, 2-mercaptobenzothiazole and 1-amino benzotriazole; (5) 0.5-3% of the total mass of the developing solution is added in the form of an organic carboxylate synergist, and stirring is performed until complete dissolution, wherein the organic carboxylate synergist is at least one selected from the group consisting of sodium citrate, potassium tartrate and sodium gluconate; (6) 0.01-1% of the total mass of the developing solution is added in the form of a surfactant, and stirring is continuously performed for 30 minutes, wherein the surfactant is at least one selected from the group consisting of acetylene glycol polyoxyethylene ether, diphenyl styryl phenol polyoxyethylene ether and 2-naphthol polyoxyethylene ether; (7) 0.05-0.5% of the total mass of the developing solution is added in the form of a pH stabilizer, wherein the pH stabilizer is at least one selected from the group consisting of tris-hydroxymethyl aminomethane and boric acid-borax buffer system, and stirring is performed for 15 minutes; (8) 0.001-0.1% of the total mass of the developing solution is added in the form of a metal chelating agent, wherein the metal chelating agent is at least one selected from the group consisting of disodium ethylenediaminetetraacetate and diethylenetriamine pentaacetate, and stirring is performed until complete dissolution; (9) The remaining amount of ultrapure water is added to the total mass of the developing solution, and stirring is performed for 10 minutes to obtain a mixed solution; (10) The mixed solution obtained in step (9) is filtered to have a particle size of ≤25 pieces / mL (≥0.1 μm); (11) The filtered developing solution is treated by a deoxygenation device; (12) The deoxygenated developing solution is divided in a clean environment, and is sealed and stored by filling with high-purity nitrogen.

[0006] Further, in steps (1) and (12), the clean environment is ISO 5. This can maximize the prevention of environmental particle pollution from the production source and the terminal dispensing link, and is a fundamental guarantee for achieving the ultra-high cleanliness target in step (10).

[0007] Further, in steps (1) and (9), the resistivity of the ultrapure water is ≥18.2 MΩ·cm. This ensures the extremely high purity of the base solvent, effectively avoiding the potential negative effects of trace ions in water on the stability of the developer, the corrosion rate of metals, and the electrical properties of semiconductor devices.

[0008] Further, in step (4), the mass ratio of at least two of 5-amino tetrazole, 2-mercaptobenzothiazole, and 1-amino benzotriazole in the metal protection agent is 1:(0.5-2). This is the best synergistic ratio range verified by optimization. Within this range, the molecules of each protection agent can achieve the best adsorption density and synergistic effect on the metal surface, thereby maximizing the corrosion prevention efficiency.

[0009] Further, in step (10), two-stage circulation filtration is performed through 0.5 μm and 0.2 μm polytetrafluoroethylene filter membranes for at least 1 hour, the temperature is maintained at 20-25°C during the filtration process, and an online particle size detector is used for real-time monitoring until the particle size is ≤25 pieces / mL (≥0.1 μm). The above components collectively form a precise and controllable ultra-clean filtration system that not only efficiently removes particulate pollutants but also ensures the scientificity and accuracy of the filtration endpoint determination, thereby stably producing a developer that meets strict standards.

[0010] Further, in step (11), the dissolved oxygen content is controlled to be ≤20 ppb. This can effectively inhibit the oxidation and corrosion of active metals such as silver by dissolved oxygen, which is a key process parameter for obtaining an extremely low silver corrosion rate (<3.5 nm / min) and ensuring long-term stability.

[0011] The application also provides a developer prepared by the method of any one of claims 1-6, wherein the corrosion rate of the developer on an aluminum layer is less than 4 nm / min, the corrosion rate of the developer on a silver layer is less than 3.5 nm / min, and the corrosion rate of the developer on a titanium layer is less than 1 nm / min; and the increase in the corrosion rate of the developer on an aluminum layer is ≤10%, the increase in the corrosion rate of the developer on a silver layer is ≤10%, and the increase in the corrosion rate of the developer on a titanium layer is ≤10% after the developer is stored at 25°C for 30 days.

[0012] The application also provides a use of the developer in the development of an exposed substrate in an AMOLED panel manufacturing process, i.e., using the above-mentioned developer to develop a substrate at 25±2°C.

[0013] Compared with the prior art, the application has the following advantages: I. The present application realizes efficient and balanced protection of various heterogeneous metals by constructing a synergistic corrosion prevention system. By compounding specific types and contents of metal protectants and cooperating with organic carboxylate salt synergists, different molecules form a dense and firm composite protective film on the surfaces of Ag, Al, Ti and other metals through synergistic adsorption, thereby efficiently isolating the chemical corrosion of the metal layer by the organic alkali in the developer. The system enables the corrosion rate of the final developer on the aluminum layer and the silver layer to be controlled below 4 nm / min, and the corrosion rate on the titanium layer is even lower than 1 nm / min, which is nearly an order of magnitude lower than that of the traditional TMAH developer (the corrosion rate on aluminum and silver is as high as about 30 nm / min), greatly reducing the damage to the Ti / Al / Ti composite metal layer and silver electrode in the AMOLED array, and improving the product yield from the source.

[0014] II. The present application ensures high precision and defect-free patterns by optimizing dissolution, wetting and developing kinetics. By introducing specific organic solvents and stepwise water addition process, it ensures that the solvent molecules and protectants, synergists, etc. are fully miscible at high concentrations in the early stage, thereby significantly enhancing the dissolution capacity and dispersion stability of the dissolved photoresist products, effectively inhibiting the re-aggregation and re-attachment of the dissolved photoresist, and avoiding development residues. Secondly, specific surfactants can significantly reduce the surface tension of the developer, greatly improving its wettability and permeability on the entire substrate surface. This not only ensures that the developer spreads quickly and uniformly, but also ensures the consistency of the developing rate in different areas of the substrate, thereby ensuring that the pattern profile after development is steep, the line width is uniform, and there is no residue contamination, meeting the stringent requirements of high-precision AMOLED panel manufacturing.

[0015] III. The present application gives the product extreme purity and ultra-long storage life by establishing multiple stabilization and purification mechanisms. Through ultra-strict filtration (particle size ≤ 25 / mL), deoxygenation treatment (dissolved oxygen ≤ 20 ppb), and nitrogen-sealed preservation in a clean environment, it ensures that the final product has extremely low particle impurity content and metal ion concentration, eliminates the risk of oxidation, and avoids introducing new sources of contamination during the developing process. At the same time, the pH stabilizer in the formula can effectively buffer the system and maintain the long-term stability of the developing alkalinity, preventing the degradation of developing performance caused by pH fluctuations. The metal chelating agent can precisely complex trace amounts of metal ions in the solution, eliminating the risk of these impurities catalyzing the decomposition of effective components and damaging the protective film. These measures work together to not only ensure the efficiency and stability of the developing effect, but also give the product excellent long-term storage stability, further improving the yield and process reliability of AMOLED panel manufacturing. BRIEF DESCRIPTION OF DRAWINGS

[0016] Figure 1SEM image of the sample in Example 1 of the present application.

[0017] Figure 2 SEM image of the sample in Comparative Example 1 of the present application. DETAILED DESCRIPTION

[0018] To enable persons skilled in the art to understand the features and effects of the present application, the following is a general description and definition of the terms and phrases mentioned in the specification and claims. Unless otherwise specified, all technical and scientific words used in the text have their usual meanings understood by those skilled in the art of the present application, and in the event of conflict, the definitions in the specification shall prevail.

[0019] The present application will be described below in the specific embodiments and examples. It should be understood that these specific embodiments and examples are merely illustrative and are not intended to limit the scope of the present application and its use.

[0020] The methods, reagents and conditions used in the following preparation examples, comparative examples and examples are conventional methods, reagents and conditions in the art, unless otherwise specified.

[0021] Unless otherwise specified, in the present application, parts by weight represent the relative mass fraction in the composition, which can be any mass unit, such as but not limited to kilogram, kilogram, gram, etc. mass unit.

[0022] The specific embodiments are described in detail below, but it should be understood that the scope of protection of the present application is not limited by the specific embodiments. The raw materials and reagents used in the examples are commercially available unless otherwise specified.

[0023] Example 1 The present embodiment provides a preparation method of a developing solution for AMOLED panel manufacturing, comprising the following steps: (1) In an ISO 5 clean environment, 44.6 kg of ultrapure water (resistivity ≥ 18.2 MΩ·cm) was added to the reaction kettle, and stirred at room temperature at a speed of 425 revolutions per minute.

[0024] (2) Slowly add 3.5 kg of tetramethylammonium hydroxide, continue to stir for 5 minutes until completely dissolved.

[0025] (3) Add 3.0 kg of dipropylene glycol methyl ether, stir until completely dissolved.

[0026] (4) Add 1.0 kg of 5-amino tetrazole and 1.0 kg of 2-mercaptobenzothiazole, stir until completely dissolved.

[0027] (5) Add 1.5 kg of sodium citrate, stir until completely dissolved.

[0028] (6) Add 0.5 kg of diphenylstyryl phenol polyoxyethylene ether, and continuously stir for 30 minutes.

[0029] (7) Add 0.25 kg of tris-hydroxymethyl aminomethane, and stir for 15 minutes.

[0030] (8) Add 0.05 kg of disodium ethylenediaminetetraacetate, and stir until completely dissolved.

[0031] (9) Add 44.6 kg of ultrapure water, and stir for 10 minutes to make the system uniform, to obtain a mixed solution.

[0032] (10) The mixed solution obtained in step (9) is subjected to circulating filtration, and is sequentially passed through polytetrafluoroethylene filter membranes with pore sizes of 0.5 μm and 0.2 μm, and is filtered at 22°C for 1.5 hours, and real-time monitoring is performed using an online particle size detector, until the particle size of the filtrate is ≤25 pieces / mL (≥0.1 μm).

[0033] (11) The filtered developer is subjected to deoxygenation treatment, and the dissolved oxygen content in the filtrate is controlled to be ≤15 ppb.

[0034] (12) The deoxygenated developer is sub-packed in an ISO 5 clean environment, and is immediately sealed after being filled with high-purity nitrogen.

[0035] Example 2 The present embodiment provides a preparation method of a developer for AMOLED panel manufacturing, comprising the following steps: (1) In an ISO 5 clean environment, 38.376 kg of ultrapure water (resistivity ≥18.2 MΩ·cm) is added to a reaction kettle, and is stirred at a rotation speed of 400 revolutions / minute at room temperature.

[0036] (2) 2.0 kg of tetramethylammonium hydroxide is slowly added, and stirring is continuously performed for 5 minutes until complete dissolution.

[0037] (3) 1.0 kg of ethylene glycol is added, and stirring is performed until complete dissolution.

[0038] (4) 0.33 kg of 2-mercaptobenzothiazole and 0.17 kg of 1-amino benzotriazole are added, and stirring is performed until complete dissolution.

[0039] (5) 0.5 kg of potassium tartrate is added, and stirring is performed until complete dissolution.

[0040] (6) 0.01 kg of acetylene glycol polyoxyethylene ether is added, and continuously stirring is performed for 30 minutes.

[0041] (7) 0.05 kg of a boric acid-borax buffer system is added, and stirring is performed for 15 minutes.

[0042] (8) Add 0.001 kg diethylene triamine pentaacetic acid, and stir until completely dissolved.

[0043] (9) Add 57.563 kg ultrapure water, and stir for 10 minutes to make the system uniform, to obtain a mixed solution.

[0044] (10) The mixed solution obtained in step (9) is subjected to circulating filtration, and is sequentially passed through polytetrafluoroethylene filter membranes with pore sizes of 0.5 μm and 0.2 μm, and is filtered at 20°C for 2.0 hours, and real-time monitoring is performed using an online particle size detector, until the particle size of the filtrate is ≤25 pieces / mL (≥0.1 μm).

[0045] (11) The filtered developer is subjected to deoxygenation treatment, and the dissolved oxygen content in the filtrate is controlled to be ≤20 ppb.

[0046] (12) The deoxygenated developer is sub-packed in an ISO 5 clean environment, and is immediately sealed after being filled with high-purity nitrogen.

[0047] Example 3 The present embodiment provides a preparation method of a developer for AMOLED panel manufacturing, comprising the following steps: (1) In an ISO 5 clean environment, 48.24 kg of ultrapure water (resistivity ≥18.2 MΩ·cm) is added to a reaction kettle, and is stirred at a rotation speed of 450 revolutions / minute at room temperature.

[0048] (2) 5.0 kg of tetramethylammonium hydroxide is slowly added, and stirring is continued for 5 minutes until complete dissolution.

[0049] (3) 5.0 kg of N-methyl-2-pyrrolidone is added, and stirring is performed until complete dissolution.

[0050] (4) 1.67 kg of 5-amino tetrazole and 3.33 kg of 1-amino benzotriazole are added, and stirring is performed until complete dissolution.

[0051] (5) 3.0 kg of sodium gluconate is added, and stirring is performed until complete dissolution.

[0052] (6) 1.0 kg of 2-naphthol polyoxyethylene ether is added, and stirring is continued for 30 minutes.

[0053] (7) 0.5 kg of tris-hydroxymethyl aminomethane is added, and stirring is performed for 15 minutes.

[0054] (8) 0.1 kg of ethylenediamine tetraacetic acid disodium is added, and stirring is performed until complete dissolution.

[0055] (9) 32.16 kg of ultrapure water is added, and stirring is performed for 10 minutes to make the system uniform, to obtain a mixed solution.

[0056] (10) The mixed solution obtained in step (9) is subjected to circulation filtration, and is filtered through polytetrafluoroethylene filter membranes with pore sizes of 0.5 μm and 0.2 μm, respectively, at 25°C for 1.0 hour, and is monitored in real time by using an on-line particle size detector until the particle size of the filtrate is ≤25 pieces / mL (≥0.1 μm).

[0057] (11) The filtered developer is subjected to deoxygenation treatment to control the content of dissolved oxygen in the filtrate to be ≤10 ppb.

[0058] (12) The deoxygenated developer is sub-packed in an ISO 5 clean environment, and is sealed after being immediately filled with high-purity nitrogen.

[0059] Example 4 The present example provides a preparation method of a developer for AMOLED panel manufacturing, comprising the following steps: (1) In an ISO 5 clean environment, 49.0 kg of ultrapure water (resistivity ≥18.2 MΩ·cm) is added to a reaction kettle, and is stirred at a rotation speed of 430 revolutions / minute at room temperature.

[0060] (2) 2.5 kg of tetramethylammonium hydroxide is slowly added, and stirring is continued for 5 minutes until complete dissolution.

[0061] (3) 1.0 kg of dipropylene glycol methyl ether and 1.0 kg of N-methyl-2-pyrrolidone are added, and stirring is continued until complete dissolution.

[0062] (4) 1.0 kg of 5-amino tetrazole, 1.0 kg of 2-mercaptobenzothiazole and 1.0 kg of 1-amino benzotriazole are added, and stirring is continued until complete dissolution.

[0063] (5) 1.0 kg of sodium citrate and 1.0 kg of potassium tartrate are added, and stirring is continued until complete dissolution.

[0064] (6) 0.05 kg of acetylenic glycol polyoxyethylene ether and 0.05 kg of diphenylstyryl phenol polyoxyethylene ether are added, and stirring is continued for 30 minutes.

[0065] (7) 0.3 kg of boric acid-borax buffer system is added, and stirring is continued for 15 minutes.

[0066] (8) 0.01 kg of disodium ethylenediaminetetraacetate is added, and stirring is continued until complete dissolution.

[0067] (9) 40.09 kg of ultrapure water is added, and stirring is continued for 10 minutes to make the system uniform, to obtain a mixed solution.

[0068] (10) The mixed solution obtained in step (9) is subjected to circulation filtration, and is filtered through polytetrafluoroethylene filter membranes with pore sizes of 0.5 μm and 0.2 μm, respectively, at 23°C for 1.8 hours, and real-time monitoring is performed using an online particle size detector until the particle size of the filtrate is ≤25 pieces / mL (≥0.1 μm).

[0069] (11) The filtered developer is subjected to deoxygenation treatment to control the content of dissolved oxygen in the filtrate to be ≤18 ppb.

[0070] (12) The deoxygenated developer is packaged under an ISO 5 clean environment, and is immediately sealed after being filled with high-purity nitrogen.

[0071] Comparative Example 1 (without adding any metal protecting agent and organic carboxylate salt synergist) Preparation method: (1) In an ISO 5 clean environment, 45.35 kg of ultrapure water was added to a reaction kettle, and stirring was performed at a rotation speed of 425 rpm at room temperature.

[0072] (2) 3.5 kg of tetramethylammonium hydroxide was slowly added, and stirring was continued for 5 minutes until complete dissolution.

[0073] (3) 3.0 kg of dipropylene glycol methyl ether was added, and stirring was performed until complete dissolution.

[0074] (4) The step of adding a metal protecting agent and an organic carboxylate salt synergist was skipped.

[0075] (5) 0.5 kg of a diphenylvinylphenol polyoxyethylene ether was added, and stirring was continued for 30 minutes.

[0076] (6) 0.25 kg of tris-hydroxymethyl aminomethane was added, and stirring was performed for 15 minutes.

[0077] (7) 0.05 kg of disodium ethylenediaminetetraacetate was added, and stirring was performed until complete dissolution.

[0078] (8) 45.35 kg of ultrapure water was added, and stirring was performed for 10 minutes to make the system uniform, to obtain a mixed solution.

[0079] (The subsequent filtration, deoxygenation, and packaging steps are the same as in Example 1) Comparative Example 2 (metal protecting agent is only a single component) Preparation method: (1) In an ISO 5 clean environment, 44.6 kg of ultrapure water was added to a reaction kettle, and stirring was performed at a rotation speed of 425 rpm at room temperature.

[0080] (2) 3.5 kg of tetramethylammonium hydroxide was slowly added, and stirring was continued for 5 minutes until complete dissolution.

[0081] (3) Add 3.0 kg of dipropylene glycol methyl ether, and stir until completely dissolved.

[0082] (4) Add 2.0 kg of 2-mercaptobenzothiazole (single protective agent), and stir until completely dissolved.

[0083] (5) Add 1.5 kg of sodium citrate, and stir until completely dissolved.

[0084] (6) Add 0.5 kg of distyrylphenol polyoxyethylene ether, and continue stirring for 30 minutes.

[0085] (7) Add 0.25 kg of tris-hydroxymethyl aminomethane, and stir for 15 minutes.

[0086] (8) Add 0.05 kg of disodium ethylenediaminetetraacetate, and stir until completely dissolved.

[0087] (9) Add 44.6 kg of ultrapure water, and stir for 10 minutes to make the system uniform, to obtain a mixed solution.

[0088] (Subsequent steps are the same as in Example 1) Comparative Example 3 (without adding an organic carboxylate salt synergist) Preparation method: (1) In an ISO 5 clean environment, add 45.35 kg of ultrapure water to a reaction kettle, and stir at a speed of 425 rpm at room temperature.

[0089] (2) Slowly add 3.5 kg of tetramethylammonium hydroxide, and continue stirring for 5 minutes until completely dissolved.

[0090] (3) Add 3.0 kg of dipropylene glycol methyl ether, and stir until completely dissolved.

[0091] (4) Add 1.0 kg of 5-amino tetrazole and 1.0 kg of 2-mercaptobenzothiazole, and stir until completely dissolved.

[0092] (5) Skip the step of adding an organic carboxylate salt synergist.

[0093] (6) Add 0.5 kg of distyrylphenol polyoxyethylene ether, and continue stirring for 30 minutes.

[0094] (7) Add 0.25 kg of tris-hydroxymethyl aminomethane, and stir for 15 minutes.

[0095] (8) Add 0.05 kg of disodium ethylenediaminetetraacetate, and stir until completely dissolved.

[0096] (9) Add 45.35 kg of ultrapure water, and stir for 10 minutes to make the system uniform, to obtain a mixed solution.

[0097] (The subsequent steps are the same as in Example 1) Comparative Example 4 (change in order of addition) Preparation method: (1) Under an ISO 5 clean environment, 89.2 kg of ultrapure water was added to a reaction kettle (all water was added at one time), and stirred at room temperature at a speed of 425 rpm.

[0098] (2) 3.5 kg of tetramethylammonium hydroxide was slowly added, and stirring was continued for 5 minutes until complete dissolution.

[0099] (3) 1.0 kg of 5-amino tetrazole and 1.0 kg of 2-mercaptobenzothiazole were added, and stirring was continued until complete dissolution. (The protective agent was added first, followed by the solvent) (4) 3.0 kg of dipropylene glycol methyl ether was added, and stirring was continued until complete dissolution.

[0100] (5) 1.5 kg of sodium citrate was added, and stirring was continued until complete dissolution.

[0101] (6) 0.5 kg of diphenylthylene phenol polyoxyethylene ether was added, and stirring was continued for 30 minutes.

[0102] (7) 0.25 kg of tris-hydroxymethyl aminomethane was added, and stirring was continued for 15 minutes.

[0103] (8) 0.05 kg of disodium ethylenediaminetetraacetate was added, and stirring was continued until complete dissolution.

[0104] (9) The step of supplementing ultrapure water was skipped.

[0105] (The subsequent steps are the same as in Example 1) Comparative Example 5 (relaxed post-treatment standards) Preparation method: (1) to (9) were exactly the same as in Example 1.

[0106] (10) The mixture obtained in step (9) was filtered once, filtered through a polytetrafluoroethylene filter membrane of 0.5 μm for 0.5 hours, without controlling the temperature, without using an online particle size detector, until it was clear to the naked eye.

[0107] (11) The step of deoxygenation device treatment was skipped.

[0108] (12) The developer was sub-packed under an ISO 7 (ten thousand level) clean environment, and directly sealed and stored, without filling with high-purity nitrogen.

[0109] Examples 1-4 (which cover all component ranges and numerical ranges) and Comparative Examples 1-5 were tested, and the testing methods were as follows: 1. Developing process: prepare the corresponding developing solution according to the specific implementation method, place the prepared developing solution in a constant temperature tank, set the temperature to 25°C. Soak the exposed substrate in the developing solution for 60s; rinse the sample with pure water and dry it with nitrogen to obtain the developed substrate. Observe the developing effect with a microscope, as shown in Figure 1 、 Figure 2 , Figure 1 is the SEM image of the sample in Example 1, and no corrosion phenomenon is observed after adding the metal protective agent; Figure 2 is the SEM image of the sample in Comparative Example 1, and the metal edge corrosion phenomenon is observed without adding the metal protective agent.

[0110] 2. Metal corrosion rate test: cut titanium, aluminum and silver sheets into 2cm x 2cm size, measure the thickness of the sample using a high-precision micrometer or an electronic balance (weight method by density and area). Take 200mL of developing solution, heat in a 25°C constant temperature water bath, immerse the sample for 30min, rinse with pure water, dry and measure the thickness, and calculate the corrosion rate of the three metals respectively, as shown in Table 1.

[0111] 3. Accelerated storage stability test Take enough developing solution newly prepared by the method of the application, strictly according to the nitrogen sealing conditions recorded in the application, divide it into multiple clean sample bottles, place the sample bottles in a constant temperature incubator, store at a temperature of 25 ± 0.5°C, avoid light and static for 30 days. After the storage period is up, take out the sample bottle, observe the physical state of the sample under natural light or a standard white light lamp box with a white background as the substrate, the solution remains clear and transparent, there is no any visible change compared with before storage, no color change (such as yellowing), no turbidity, no suspended matter, no precipitation or crystallization precipitation is qualified, and any visible color change (such as yellowing), turbidity, suspended matter, precipitation or stratification of the solution is unqualified.

[0112] 4. Comparison test of metal corrosion rate before and after storage The same as the test of fresh developing solution, high-purity aluminum, silver and titanium sheets (for example, purity ≥ 99.99%) are used, cut into a specified size (for example, 2 cm × 2 cm), and the initial average thickness (d0) of each sheet is accurately measured using a high-precision thickness gauge (for example, a four-probe square resistance tester combined with a film thickness gauge, or directly using a high-precision micrometer / electronic balance to calculate by weighing method). Take 200 mL of freshly prepared developing solution and place it in a constant temperature water bath, maintaining the temperature at 25 ± 0.5℃, immerse the metal sheet with pre-measured thickness into the developing solution, ensuring complete coverage by the liquid, and soak for 30 minutes. Take out the metal sheet, rinse thoroughly with ultrapure water, dry with high-purity nitrogen, and measure the average thickness of the metal sheet again (d1), and calculate the initial corrosion rate (nm / min) as (d0 - d1) / 30. From the same batch of developing solution stored for 30 days, take out a bottle and immediately test after opening, repeat the above steps using the stored developing solution and new metal sheets of the same batch, and measure the corrosion rate after storage. Calculate the increase in corrosion rate for each metal, and the results are shown in Table 2.

[0113] Table 1 Aluminum corrosion rate nm / min Silver corrosion rate nm / min Titanium corrosion rate nm / min Developing property Example 1 3.1 2.5 ＜1 Excellent, no residue Example 2 3.8 3.4 ＜1 Good Example 3 2.8 2.2 ＜1 Excellent, no residue Example 4 3.0 2.7 ＜1 Excellent, no residue Comparative Example 1 35.1 29.8 1.5 Good Comparative Example 2 4.5 16.3 ＜1 Good Comparative Example 3 5.2 8.1 ＜1 Good Comparative Example 4 3.3 2.8 ＜1 Poor, residue Comparative Example 5 3.2 2.9 ＜1 Good, but increased defects Table 2 Increase in aluminum corrosion rate after 30 days Increase in silver corrosion rate after 30 days Appearance after 30 days of storage Example 1 5% 4% Clear and transparent, no change Example 2 8% 7% Clear and transparent, no change Example 3 3% 3% Clear and transparent, no change Example 4 6% 5% Clear and transparent, no change Comparative Example 1 - - - Comparative Example 2 15% 45% Slightly yellow solution with flocculation Comparative Example 3 18% 25% Slightly yellow solution Comparative Example 4 10% 9% Clear and transparent Comparative Example 5 20% 35% Solution significantly yellowed Based on the results of Tables 1 and 2, it can be seen that: 1. Regarding corrosion resistance: Comparative Example 1 does not contain a protection system at all, and its corrosion rate is extremely high, proving the necessity of adding a corrosion protection system to the TMAH system. The corrosion rates of Comparative Examples 2 (single protective agent) and 3 (without synergist) are significantly higher than all the examples, especially the silver corrosion rate and its increase after storage. This proves the key and irreplaceable role of the synergistic effect of "composite metal protective agent" and "organic carboxylate synergist", solving the industry's difficult problem of "trade-off" with single components.

[0114] The principle of the poor effect of Comparative Example 2 (single protective agent) lies in the inherent limitations of adsorption specificity, film integrity and chemical stability of a single corrosion inhibitor molecule in dealing with heterogeneous metal surfaces. Specifically, 2-mercaptobenzothiazole (MBT) mainly coordinates and adsorbs with metals through sulfur and nitrogen atoms, and it has a certain affinity for silver, but its adsorption capacity for aluminum and titanium with dense oxide layers on the surface is weak, resulting in the inability to form a complete protective layer on the Ti / Al / Ti / Ag composite metal system. More importantly, the single MBT molecule forms a single-molecule film with uniform structure, and the molecular configuration is fixed, which cannot effectively cover all the high-activity sites on the metal surface, resulting in micro "voids" in the film layer, and OH⁻ and dissolved oxygen in the developer can penetrate these defect sites to cause local corrosion. In contrast, the composite protective agent (such as the combination of MBT and 5-methylbenzotriazole MBTA) of the present application produces a molecular synergistic effect. The MBTA molecule has good planarity and strong complexing ability with silver; when they coexist, they can co-adsorb and interweave on the metal surface to form a more dense and firm "composite multi-dimensional protective film", achieving "taking advantage of each other's strengths" and "no dead angle protection" for different metals. In addition, the structure of the composite film enhances its overall chemical inertness, and combined with the stabilizing effect of the organic carboxylate synergist, it significantly improves the long-term durability of the protective system in alkaline environments.

[0115] 2. Regarding process stability: Comparative Example 4 changes the feeding order, resulting in residues after development, which proves that the specific feeding order of "stepwise water addition, base first and then protective agent" is crucial for ensuring the full dissolution of all components, the realization of functions, and the avoidance of mutual interference.

[0116] 3. Regarding product purity and storage stability: Comparative Example 5 relaxes the post-treatment standard, and its corrosion rate increases significantly after storage and the solution discolors, which proves that the series of post-treatment processes such as "ultra-filtration (≤25 pieces / mL)", "deep deoxygenation (≤20 ppb)", and "nitrogen-filled sealing" play a decisive role in preventing performance degradation of the product during storage and maintaining long-term stability.

[0117] In summary, through systematic comparison of the examples and comparative examples, it is fully proved that the technical solution of the present application is an indivisible organic whole, and its excellent comprehensive performance (low corrosion, no residue, high uniformity, long shelf life) is inseparable from the joint contribution of the synergistic corrosion protection of the composite protective agent and the synergist, the system stability guaranteed by the specific feeding order, and the ultra-high purity achieved by the extreme post-treatment process. This is in sharp contrast to the defects of the prior art, highlighting the significant progress and creativity of the present application.

[0118] It should be understood that the above embodiments are only to illustrate the technical concept and characteristics of the present application, and the purpose is to enable those skilled in the art to understand the content of the present application and to implement it, and it cannot be considered that the specific implementation of the present application is limited to these descriptions. For ordinary skilled in the art to which the present application belongs, without departing from the concept of the present application, some simple deductions or substitutions can be made, and any equivalent changes or modifications made according to the spirit and essence of the present application should be covered within the protection scope of the present application.

Claims

1. A method for preparing a developer for AMOLED panel manufacturing, characterized in that, The method comprises the following steps: (1) under a clean environment, adding 40-60% of the total mass of the developer of ultrapure water into a reaction kettle, stirring at a speed of 400-450 rpm at room temperature; (2) adding 2-5% of the total mass of the developer of organic base, continuously stirring for 5 minutes until completely dissolved, the organic base being a quaternary ammonium base organic compound, specifically tetramethylammonium hydroxide; (3) adding 1-5% of the total mass of the developer of organic solvent, stirring until completely dissolved, the organic solvent being at least one selected from dipropylene glycol methyl ether, ethylene glycol, and N-methyl-2-pyrrolidone; (4) adding 0.5-5% of the total mass of the developer of metal protective agent, stirring until completely dissolved, the metal protective agent being composed of at least two of 5-amino tetrazole, 2-mercaptobenzothiazole, and 1-amino benzotriazole; (5) adding 0.5-3% of the total mass of the developer of organic carboxylate synergist, stirring until completely dissolved, the organic carboxylate synergist being at least one selected from sodium citrate, potassium tartrate, and sodium gluconate; (6) adding 0.01-1% of the total mass of the developer of surfactant, continuously stirring for 30 minutes, the surfactant being at least one selected from acetylenic glycol polyoxyethylene ether, diphenylstyryl phenol polyoxyethylene ether, and 2-naphthol polyoxyethylene ether; (7) adding 0.05-0.5% of the total mass of the developer of pH stabilizer, the pH stabilizer being at least one selected from tris-hydroxymethyl aminomethane and boric acid-borax buffer system, stirring for 15 minutes; (8) adding 0.001-0.1% of the total mass of the developer of metal chelating agent, the metal chelating agent being at least one selected from disodium ethylenediaminetetraacetate and diethylenetriamine pentaacetic acid, stirring until completely dissolved; (9) adding the remaining amount of ultrapure water to the total mass of the developer and stirring for 10 minutes to obtain a mixed solution; (10) filtering the mixed solution obtained in step (9) to a particle size of ≤25 pieces / mL (≥0.1 μm); (11) treating the filtered developer with a deoxygenation device; (12) performing aseptic packaging of the deoxygenated developer under a clean environment and sealing and storing the developer by filling high-purity nitrogen.

2. The method of claim 1, wherein: In steps (1) and (12), the clean environment is ISO 5.

3. The method of claim 1, wherein: In steps (1) and (9), the ultrapure water has a resistivity of ≥18.2 MΩ·cm.

4. The method of claim 1, wherein: In step (4), the mass ratio of the at least two of 5-amino tetrazole, 2-mercaptobenzothiazole, and 1-amino benzotriazole in the metal protective agent is 1:(0.5-2).

5. The method of claim 1, wherein: In step (10), the solution is filtered through two-stage circulation filtering with 0.5 μm and 0.2 μm polytetrafluoroethylene filter membranes for at least 1 hour, the filtering process is performed at a temperature of 20-25 °C, and an online particle size detector is used for real-time monitoring until the particle size is ≤25 pieces / mL (≥0.1 μm).

6. The method of claim 1, wherein: In step (11), the dissolved oxygen content is controlled to be ≤20 ppb.

7. A developer prepared by the method of any one of claims 1-6.

8. The developer according to claim 7, characterized by: The etching rate of the developing solution to the aluminum layer is less than 4 nm / min, the etching rate to the silver layer is less than 3.5 nm / min, and the etching rate to the titanium layer is less than 1 nm / min.

9. The developer according to claim 7, characterized by: After the developing solution is stored at 25 DEG C in a sealed state for 30 days, the increase of the etching rate to the aluminum layer is less than or equal to 10%, the increase of the etching rate to the silver layer is less than or equal to 10%, and the increase of the etching rate to the titanium layer is less than or equal to 10%.

10. Use of a developer for developing a substrate after exposure in an AMOLED panel manufacturing process, characterized in that: The substrate is developed by immersion at 25+ / -2 DEG C using the developing solution as claimed in claims 7 to 9.

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