A high-efficiency CF developer composition

Abstract

The present invention discloses an efficient CF developer composition for high-generation line technology in the display field. By adding a specific Gemini surfactant, the uniform and stable effect of the basic group and the photoresist molecule is effectively promoted, and the development accuracy is improved. The developer system has strong stability and excellent solubility for the photoresist molecules after development. The developer has fast development speed, good image clarity and accuracy, stable CD value, wide production and use temperature range, and is suitable for the current high-generation line technology.

Description

Technical Field

[0001] The invention relates to a high-efficiency CF developer composition for high-generation line technology in the display field, which is used for developing various negative photoresists in CF process in TFT manufacturing technology. Background Art

[0002] In the field of flat panel display, especially in large-size display devices, TFT-LCD technology is the current mainstream process. In the photolithography process of TFT-LCD color filter manufacturing, in order to obtain the required fine images, it is necessary to use photoresist to form a thin film on the substrate, and then block and expose it with a mask of a specific pattern. The photoresist is composed of a pigment dispersion, a solvent, a photosensitive resin and related additives. The short-chain molecules containing polymers will cross-link into long-chain molecules due to light. The developer is used to develop and remove the unexposed soluble resin part to obtain the required image. The CF process is divided into multiple processes such as black matrix layer (BM), color photoresist layer (R, G, B), gap column layer (PS) and protective layer (OC). Each process has a complete photolithography process: cleaning, gluing, soft baking, exposure, development, hard baking, and then the accurate pattern is obtained after detection before proceeding to the next step. Therefore, it is crucial to the yield of the product to have a developer that can improve the developing speed, improve the clarity and accuracy of the graphics, stabilize the CD value, meet the low-foaming performance of high-pressure spraying in the process, and have no residual and easy-to-develop properties.

[0003] At present, the mainstream CF process developer on the market is mainly alkaline developer, and its main components include alkaline substances, surfactants and high-purity water. However, with the current market popularization of 4k images and the future development of 8k images, higher requirements are placed on the development accuracy in the technical process, and accurate images need to be formed after development. In order to improve the poor imaging due to the presence of undeveloped particles or undissolved substances, a more efficient developer is needed to meet the process requirements. Patent CN200810240377.9 mentions an alkaline developer containing a fluorine surfactant, which can sharply reduce the interfacial surface tension by adding a fluoride surfactant, forming excellent wetting properties and improving the development accuracy. However, the developer system composed of the surfactant has a low turbidity point, poor alkali resistance and temperature resistance, high requirements for condition control in the actual process, and production and transportation will increase additional costs. In order to further improve the surface tension of the surfactant at the interface, improve the development effect, obtain higher graphic accuracy and development speed, and meet the use of the developer in the existing equipment process, a higher demand is also put forward for the new developer composition. Summary of the invention

[0004] The main technical problem solved by the present invention is to provide an efficient CF developer composition for high-generation line processes in the display field. By adding a specific Gemini surfactant, the uniform and stable effect of the alkaline group and the photoresist molecule is effectively promoted, and the development accuracy is improved. At the same time, the addition of organic additives enhances the solubility of the soluble resin after the reaction, and the developer system has strong stability, avoiding the formation of residues, and the developer composition also has excellent stability under high alkalinity conditions.

[0005] In order to solve the above problems, the present invention adopts the following technical solutions.

[0006] A high-concentration CF developer composition for use in the field of display panels, the composition is as follows, measured by mass percentage:

[0007] 5%-20% alkaline substances,

[0008] 5%-20% Gemini surfactant,

[0009] 10%-20% organic additives,

[0010] 50%-75% deionized water.

[0011] The sum of the total mass fraction is 100%;

[0012] In the above-mentioned high-efficiency CF developer composition, the alkaline substance is one or both selected from potassium hydroxide and sodium hydroxide, wherein potassium hydroxide is preferred. The unexposed resin groups have acidic groups, which will react with the OH groups ionized by the inorganic base. - When the mass percentage of inorganic base is less than 5%, OH in the system - If the concentration is too low, the development effect will be affected, resulting in a large number of defects; when the content is higher than 20%, too strong alkalinity will reduce the cloud point of the surfactant, resulting in instability of the developer composition.

[0013] In the above-mentioned high-efficiency CF developer composition, the Gemini surfactant is represented by structural formula 1:

[0014] The benzene ring structure of the Gemini sodium disulfate surfactant of formula 1 is similar to the molecular structure of the photoresist, and has a good solubilizing effect; the Gemini structure is both rigid and flexible, and the excellent wettability and permeability can make the long hydrophobic chain spread to the reaction interface, anchor the soluble photoresist on the surface of the substrate, and encapsulate the swollen and detached small molecule photoresist molecules to prevent the photoresist molecular particles from aggregating due to electrostatic adsorption to form secondary pollution and blockage; the sodium sulfate group can increase the turbidity point of the surfactant, and can greatly improve the stability of the developer system at high alkalinity and high temperature. When the content of Gemini sodium disulfate surfactant is less than 5%, the improvement of the development effect is not obvious, and it is difficult to completely remove the soluble photoresist. When the content is higher than 20%, it hinders the activity of inorganic alkali metal ions, which will also lead to slow development speed and reduced precision.

[0015] In the above-mentioned high-efficiency CF developer composition, the organic auxiliary agent is benzyl methyl sulfone. Benzyl methyl sulfone is a polar sulfide. When it reacts with the photoresist layer, it has excellent wetting performance and dissolving power. It can quickly penetrate into the photoresist molecules, causing a swelling effect, which is more conducive to quickly removing the unexposed soluble resin and increasing the solubility of the developer system to the soluble photoresist. When the content of benzyl methyl sulfone is less than 10%, it is difficult to exert its effect; when the content is higher than 20%, it will reduce its compatibility with inorganic alkalis, which will affect the ability to remove the unexposed soluble resin.

[0016] In the above-mentioned high-efficiency CF developer composition, the deionized water is electronic grade deionized water, and its resistivity is not less than 18 MΩ at 25°C.

[0017] The significant advantage of the present invention is that by adding a specific Gemini surfactant, the uniform and stable effect of the alkaline group and the photoresist molecule is effectively promoted, thereby improving the development accuracy. At the same time, the addition of the organic auxiliary agent enhances the solubility of the soluble resin after the reaction, and the developer system has strong stability, avoiding the formation of residues, and the stability of the developer composition under high alkalinity conditions is also excellent. The production and transportation costs of the developer are effectively reduced, and the development performance of the developer is ensured not to change during use and mixing. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1 The figure is a synthetic flow chart of the Gemini sodium disulfate surfactant of the present invention. DETAILED DESCRIPTION

[0019] The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. The exemplary implementation modes of the present invention and their description are only used to explain the present invention and are not intended to limit the present invention.

[0020] The preparation method of Gemini sodium disulfate surfactant comprises the following steps:

[0021] 1) Under nitrogen protection, add 0.01 mol NaH to a 200 mL three-necked flask, heat to 60°C, dropwise add 0.05 mol 3-phenyl-1,5-pentanediol solution dissolved in butyl acetate, and stir thoroughly to dissolve the NaH.

[0022] Continue to raise the temperature to 75°C, add 0.12 mol of 1,2-epoxydodecane, maintain the temperature after the addition, and follow the reaction by TLC after 24 hours. When the reaction is complete, add 0.01 mol of dilute hydrochloric acid to terminate the reaction. Pour the reaction solution into a separatory funnel, extract it three times with 300 mL of dichloromethane and 300 mL of saturated brine, combine the organic phases, dry them over anhydrous sodium sulfate for 8 hours, filter, and spin-dry the solvent to obtain intermediate A. It can be purified by recrystallization from butyl acetate.

[0023] 2) 0.04 mol of intermediate A, 120 mL of dichloromethane and 0.16 mol of anhydrous sodium carbonate are placed in a three-necked flask with a hydrogen chloride absorption device, the temperature is controlled below 5°C in an ice-salt bath, and 0.16 mol of dichloromethane solution of chlorosulfonic acid is slowly added dropwise under magnetic stirring. After the addition, the temperature and stirring are maintained for 2 hours, the ice-salt bath is removed and stirred at room temperature for 2 hours, and the mixture is neutralized with an ethanol solution of NaOH to a neutral pH. The solvent is removed by rotation, and the Gemini sodium disulfate surfactant is obtained by recrystallization twice with an ethanol-water (2:1) mixed solution. Its characterization data are as follows: 1 H NMR(300MHz, DMSO-d6), δ:0.88(t,6H,CH3),1.26(s,32H,CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2),1.40(d,4H,CH2 ),1.50-1.54(m,8H,CH2-CH2),2.58(t,1H,CH),3.38-3.62(m,8H,CH2),4.90(m,2H,CH),7.19-7.32(m,5H,C6H5),

[0024] 13C NMR (125MHz, DMSO-d6), δ: 14.1, 22.7, 25.4, 27.4, 29.6, 39.1, 46.1, 71.3, 74.3, 88.7, 125.9, 128.1, 128.5, 141.6;

[0025] HRMS calculated value C 37 H 66 O 10 Na2S2 m / z:781.02, measured value 781.00.

[0026] Examples and Comparative Examples: High-efficiency CF developer composition for use in the field of display panels.

[0027] According to the composition and mass percentage shown in Table 1 below, the high-efficiency CF developer composition of the embodiment and the comparative example was prepared respectively, and the preparation method thereof is as follows: first add deionized water into the stirring kettle at room temperature, and then add the inorganic base, organic auxiliary agent, and Gemini sodium disulfate surfactant in sequence at a rotation speed of 80r / m. After each material is added, stir until the system is clear before adding the next material; after all are added, continue stirring for 30 minutes. Then filter through two filter elements with pore sizes of 2μm and 0.5μm in sequence to finally obtain the developer. If the developer composition is still milky white and turbid and not clarified after the last 30 minutes of stirring, it is considered that the system is unstable.

[0028] Table 1

[0029]

[0030]

[0031] BMS - Benzyl Methyl Sulfone

[0032] FMES - Sulfonate of fatty acid methyl ester ethoxylate (Xihe Chemical)

[0033] Triton X-100——Polyethylene glycol monooctylphenyl ether (Triton X-100) (Haian Petrochemical)

[0034] MOA-9P——Fatty alcohol ether phosphate (Haian Petrochemical)

[0035] DMSO-Dimethyl sulfoxide

[0036] PVS-phenyl vinyl sulfone

[0037] Experimental example: Experiment on measuring the developing performance of developer

[0038] In order to evaluate the developing performance of several CF developer compositions in the above Examples 1-6 and Comparative Examples 1-8, the developing performance test of the developer was carried out by the following test.

[0039] 1. Manufacturing test pieces

[0040] In order to evaluate the developing performance of the high-concentration CF developer composition on the photoresist, the test piece used was a 1.5um BM negative photoresist film spin-coated on a 5cm×5cm glass substrate. The specific treatment was as follows: the glass substrate was first cleaned with a special cleaning agent, then washed with ultrapure water and dried. Then, the BM photoresist was spin-coated on the substrate at 300 speeds by a spin coater, and most of the solvent was removed by vacuuming, and then cured in an oven at 100°C for 150s. The mask pattern of a certain line width was transferred to the test piece by an exposure machine, thereby obtaining a 1.5um thick BM photoresist test piece for testing the developing performance of the high-concentration CF developer composition.

[0041] 2. Development test

[0042] Dilute the high-concentration CF developer composition with high-purity water by 100-400 times, adjust the temperature to 23°C, and spray the diluted developer on the BM photoresist test piece with a constant pressure for 60 seconds, then rinse with high-purity water and dry with nitrogen. Direct observation under a microscope:

[0043] 1. Is the developed image clear?

[0044] 2. Check whether there are burrs on the edges of the graphics.

[0045] 3. Is there any photoresist residue?

[0046] 4. Whether there is corrosion on the glass substrate.

[0047] At the same time, the line width CD value of the line on the BM photoresist test piece is measured and compared with the line width CD value of the mask (line width standard 10μm) to observe whether there is underdevelopment or overdevelopment.

[0048] The judging criteria are as follows:

[0049] 5.10±0.30μm qualified

[0050] The developer solution after development was filtered through 0.2 μm filter paper to observe whether clogging occurs.

[0051] 6. If the filter paper is clogged, it is unqualified

[0052] The test results are shown in Table 2.

[0053] Table 2

[0054]

[0055] It can be seen from Table 1 and Table 2 that under high alkalinity conditions, there are few surfactants that can meet the stability of the system. The developer with an unstable system will have concentration differences during production, transportation and use, resulting in extremely unstable development effects. Therefore, Comparative Examples 2 and 3 are unqualified. The pH of Comparative Example 1 is too low, so the development effect is very poor. Comparative Example 4 uses a highly alkali-resistant fatty alcohol ether phosphate surfactant. Although the developer system is stable under high alkalinity conditions, its molecules do not have a twin structure, and the promotion of interfacial reactions is insufficient, and the development effect is difficult to meet the requirements. Comparative Example 5 does not add a surfactant, and directly uses a strong base reaction. In addition to the swelling effect of BMS on the photoresist, the development speed is too fast to control, and the pattern is incomplete. Comparative Example 6 does not add BMS. Except for a few small burrs in the pattern, the development basically meets the requirements, but its solubility in photoresist molecules is slightly weak, resulting in clogging of the filter element. Comparative Examples 7 and 8 also use sulfone solvents, but the development effect and solubility of photoresist molecules do not reach the effect of BMS.

[0056] In summary, the positive and progressive effects of the present invention are: providing an efficient CF developer composition for high-generation line processes in the display field, by adding a specific Gemini surfactant, effectively promoting the uniform and stable effect of the alkaline group and the photoresist molecule, and improving the development accuracy. At the same time, the addition of organic additives enhances the solubility of the soluble resin after the reaction, and the developer system has strong stability, avoiding the formation of residues. The stability of the developer composition under high alkalinity conditions is also excellent, and more costs can be saved in production, transportation and use by increasing alkalinity concentration.

[0057] The above embodiments describe the present invention in detail, but they are only examples and do not limit the patent scope of the present invention. Any equivalent modification and substitution of the present invention using the present description is also within the scope of the present invention and is included in the patent protection scope of the present invention.

Claims

1. A high-efficiency CF developer composition, characterized in that: In terms of mass percentage, its composition is as follows: 5%-20% alkaline substances, 5%-20% Gemini surfactant, 10%-20% organic additives, 50%-75% deionized water, The sum of the total mass fraction is 100%; The alkaline substance is one or both of potassium hydroxide and sodium hydroxide; The Gemini surfactant is a Gemini sodium disulfate surfactant, and its structural formula is as follows: ； The organic auxiliary agent is benzyl methyl sulfone.

2. The high-efficiency CF developer composition according to claim 1, characterized in that: The resistivity of the deionized water is not less than 18 MΩ at 25°C.

3. A method for preparing a high-efficiency CF developer composition according to any one of claims 1 to 2, characterized in that: First add deionized water into the stirring kettle at room temperature, and then add alkaline substances, organic additives, and Gemini sodium disulfate surfactants in sequence at a rotation speed of 80r / m. After each material is added, stir until the system is clarified before adding the next material; after all the additions are completed, continue stirring for 30 minutes, and then filter through two filter elements with pore sizes of 2μm and 0.5μm in sequence to finally obtain a high-efficiency CF developer composition.

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