Crown ether type surfactant, preparation method thereof and photoresist developing solution

Abstract

The invention discloses a crown ether type surfactant, a preparation method thereof and a photoresist developing solution, and belongs to the technical field of photoresists. The crown ether type surfactant is more tightly combined with photoresist molecules through the pi-pi action of an intermolecular benzene ring, so that the developing solution is more easily and uniformly covered on the surface of a negative film; the crown ether type surfactant and the imidazole type surfactant in the photoresist developing solution interact with each other and have synergistic interaction, so that the surface tension of the developing solution is effectively reduced, the contact angle can be rapidly reduced in the dynamic use process, few bubbles are generated, the bubbles are rapidly removed, and the wettability of the developing solution is improved; the developing capacity of the developing solution is improved, the service life of the developing solution is guaranteed, the developing speed is stabilized, and the developing solution is low in irritation, easy to rinse, environment-friendly and capable of meeting the environment-friendly requirement.

Description

Technical Field

[0001] The invention belongs to the technical field of photoresists, and in particular relates to a crown ether type surfactant and a preparation method thereof, and a photoresist developer. Background Art

[0002] In the developer, organic bases or inorganic alkaline compounds are usually used as the main components to dissolve the photoresist. However, if only a simple combination of water and alkaline components is used, it is often difficult for the developer to quickly and evenly cover the entire surface of the photoresist due to the high surface tension of this combination. This uneven spreading will lead to imbalance in the development process, and some areas may be underdeveloped or overdeveloped. As a result, the edges of the graphics after development are often not neat, which has an adverse effect on subsequent processes.

[0003] The patent application with publication number CN118884786A discloses a negative photoresist developer composition, a preparation method and an application thereof. The negative photoresist developer composition comprises, by mass, 0.1-34 parts of an amidine compound, 2-18 parts of a compounded solubilizer, 0.8-32 parts of a Gemini surfactant, 0.1-8 parts of a buffer, 0.5-20 parts of an anti-fouling promoter, and 0.4-7 parts of a leveling regulator; wherein the compounded solubilizer comprises an organic acid ammonium and an ionic liquid; the developer is mainly used to solve the anti-corrosion problem of various substrates or metal layers, but the developing effect is still unsatisfactory. Summary of the invention

[0004] The purpose of the present invention is to provide a crown ether surfactant and a preparation method thereof to solve the problem of unbalanced development of a developer, and to provide a photoresist developer to solve the problem of poor photoresist development effect.

[0005] The purpose of the present invention can be achieved by the following technical solutions:

[0006] In a first aspect, the present invention provides a crown ether type surfactant, the chemical structural formula of the crown ether type surfactant is as follows:

[0007] In the formula, x is an integer from 1 to 3; y is an integer from 1 to 3; and m is an integer from 5 to 15.

[0008] Preferably, x is 2, y is 2, and m is 10.

[0009] Preferably, x is 1, y is 2, and m is 12.

[0010] In a second aspect, the present invention provides a method for preparing a crown ether type surfactant, comprising the following steps:

[0011] Add diaminodibenzocrown ether, alkyl carboxylic acid and carboxyl activator into an organic solvent in a molar ratio of 1:2-2.5:2.2-3, mix well, and react at a constant temperature of 55-70°C for 4-7 hours. After the reaction is completed, filter, remove part of the solvent by rotary evaporation, and then purify by column chromatography, remove the eluent by rotary evaporation to obtain a crown ether type surfactant.

[0012] Preferably, the diaminodibenzo crown ether is one of diaminodibenzo-14-crown ether-4, diaminodibenzo-15-crown ether-5 and diaminodibenzo-18-crown ether-6.

[0013] Preferably, the alkyl carboxylic acid is one of hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid and hexadecanoic acid.

[0014] Preferably, the organic solvent is one or more of diethyl ether, carbon disulfide, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide and n-butanol.

[0015] Preferably, the carboxyl activator is one or more of N-hydroxysuccinimide, 1-ethyl-(3-dimethylaminopropyl)carbodiimide and N,N-dicyclohexylcarbodiimide.

[0016] In a third aspect, the present invention provides a photoresist developer, which is composed of the following raw materials in percentage by mass: 0.5%-1.5% tetraethylammonium hydroxide, 0.1%-0.5% diethylamine, 0.5%-2% of the above-mentioned crown ether type surfactant or the crown ether type surfactant prepared by the above-mentioned preparation method, 0.1%-0.5% of imidazole type surfactant, 0.1%-2% corrosion inhibitor, 0.05%-0.5% accelerator, and the balance is water.

[0017] Preferably, the mass ratio of the crown ether surfactant to the imidazole surfactant is 2-4:1.

[0018] Preferably, the imidazole-type surfactant is 1-dodecyl-3-methyl-imidazolium bromide and / or 1-hexadecyl-3-methyl-imidazolium chloride.

[0019] Due to the delocalized electronic structure on the imidazole ring and the hydrogen bonding between the imidazole rings, imidazole-type surfactants can spontaneously aggregate in water to form aggregates of various structures, increasing the contact area between the developer and the photoresist surface, thereby improving the wettability and permeability of the developer to the photoresist surface, making the development process more comprehensive and uniform.

[0020] Preferably, the imidazole-type surfactant is obtained by mixing 1-dodecyl-3-methyl-imidazolium bromide and 1-hexadecyl-3-methyl-imidazolium chloride in a mass ratio of 5:2-5.

[0021] Preferably, the corrosion inhibitor is one or more of benzotriazole, methimazole, N-(3-aminopropyl)morpholine, 5-aminotetrazolyl, 2,4-dihydroxypyrimidine and hydroxylated naphthoquinone.

[0022] Preferably, the accelerator is one or more of cinnamic acid, caffeic acid and phenylalanine.

[0023] In an alkaline environment, the accelerator will form a strong base weak acid salt, which can reduce the initial concentration of hydroxide ions in the developer, making the initial rate of dissolution of the photoresist by the developer lower. As the photoresist dissolves, the acid ions in the strong base weak acid salt will hydrolyze into hydroxide ions, which is beneficial for the photoresist to maintain a relatively stable dissolution rate throughout the development process, improve the uniformity and stability of the development, and ensure high-quality development effects.

[0024] Beneficial effects of the present invention:

[0025] 1. The structure of the crown ether surfactant of the present invention is composed of two hydrophilic amide groups, two hydrophobic long carbon chain alkyl groups and a linking group, wherein the linking group is a benzocrown ether ring. In a developer, the crown ether ring of the benzocrown ether is hydrophobic on the outside and hydrophilic on the inside, and the relatively large volume of the benzocrown ether ring can reduce the repulsive tendency between the hydrophilic groups of the crown ether surfactant, shorten the distance between the hydrophobic chains, and the chemical bonds of the benzocrown ether ring do not destroy the hydrophilicity, which greatly promotes the crown ether surfactant to be better dissolved in the developer; at the same time, the introduction of the benzocrown ether ring increases the distance between the crown ether surfactant molecules, the surfactant molecules on the air / liquid interface are arranged loosely, the surface tension is reduced, and the defoaming speed is improved; in addition, on the surface of the photoresist with benzene ring as the main structure, the crown ether surfactant of the present invention is more closely combined with the photoresist molecules through the π-π action of the intermolecular benzene ring, so that the developer is easier to evenly cover the surface of the film, ensuring the uniformity of the development, thereby ensuring the pattern accuracy.

[0026] 2. The developer of the present invention comprises tetraethylammonium hydroxide, diethylamine, a crown ether surfactant, an imidazole surfactant, a corrosion inhibitor and an accelerator. Tetraethylammonium hydroxide and diethylamine are used as main alkaline agents to prevent incomplete dissolution of residues in the unexposed part, which is superior to inorganic alkalis and will not introduce polluting ions to affect the electrical properties and manufacturing yield of the device. The crown ether surfactant and the imidazole surfactant interact with each other and synergize to effectively reduce the surface tension of the developer. During dynamic use, the contact angle can be quickly reduced, less bubbles are generated and quickly defoamed, the wettability of the developer is improved, the developing ability of the developer is improved, the service life of the developer is guaranteed, the developing speed is stabilized, and the developer has low irritation, is easy to rinse, is environmentally friendly, and meets environmental protection requirements. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] The present invention will be further described below in conjunction with the accompanying drawings.

[0028] Figure 1 is the hydrogen spectrum corresponding to the crown ether type surfactant prepared in Preparation Example 1 of the present invention;

[0029] Figure 2 is the hydrogen spectrum corresponding to the crown ether type surfactant prepared in Preparation Example 2 of the present invention;

[0030] Figure 3 is a scanning electron microscope image of a photoresist test piece treated with the developer obtained in Example 1 of the present invention;

[0031] Figure 4 is an optical microscope image of a photoresist test piece treated with the developer obtained in Example 1 of the present invention;

[0032] Figure 5 is a scanning electron microscope image of a photoresist test piece treated with the developer obtained in Comparative Example 4 of the present invention;

[0033] Figure 6 It is an optical microscope image of the photoresist test piece after being treated with the developer obtained in Comparative Example 4 of the present invention. DETAILED DESCRIPTION

[0034] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0035] Preparation Example 1

[0036] The preparation of crown ether type surfactant comprises the following steps:

[0037] 0.1 mol of trans-4,4'-diaminodibenzo-18-crown-6 (CAS No. 32082-45-4), 0.21 mol of undecanoic acid and 0.22 mol of N,N-dicyclohexylcarbodiimide were added to 1000 mL of N,N-dimethylformamide, mixed evenly, and reacted at 55°C for 4 hours. After the reaction was completed, the mixture was filtered, and some solvents were removed by rotary evaporation. The mixture was purified by column chromatography (the eluent was a mixed solvent of benzene / ether, and the volume ratio of the two was 4:6). The eluent was removed by rotary evaporation to obtain a crown ether surfactant with a yield of 96.8%.

[0038] The chemical structural formula of the crown ether surfactant obtained is as follows:

[0039]

[0040] H NMR spectrum ( Figure 1 )Analysis: 1H NMR (500MHz, chloroform-d) δ9.13 (s, 1H), 7.14 (s, 1H), 6.93 (dd, J = 9.0, 2.2Hz, 1H), 6.77 (d, J = 8.9Hz, 1H), 4.20 (td, J = 5.0, 1.7Hz, 4H), 3.77 (td, J = 5.0, 1.8Hz, 4H), 2.33 (t, J = 8.3Hz, 2H), 1.70-1.62 (m, 2H), 1.35-1.26 (m, 13H), 0.92-0.85 (m, 3H); the peak at 9.13 is the characteristic absorption peak of the imino group in the amide group.

[0041] Preparation Example 2

[0042] The preparation of crown ether type surfactant comprises the following steps:

[0043] 0.1 mol 4′,4″(5″)-diaminodibenzo-15-crown-5 (CAS No. 245086-08-2), 0.25 mol tridecanoic acid and 0.28 mol N-hydroxysuccinimide were added to 1000 mL of chloroform, mixed evenly, and reacted at 70°C for 6 hours. After the reaction was completed, the mixture was filtered, and some solvents were removed by rotary evaporation. The mixture was purified by column chromatography (the eluent was a mixed solvent of cyclohexane / ethyl acetate, and the volume ratio of the two was 1:1). The eluent was removed by rotary evaporation to obtain a crown ether surfactant with a yield of 97.5%.

[0044] The chemical structural formula of the crown ether surfactant obtained is as follows:

[0045]

[0046] H NMR spectrum ( Figure 2)Analysis: 1H NMR (500MHz, chloroform-d) δ9.13 (s, 1H), 7.15 (d, J = 1.9 Hz, 1H), 6.93 (dd, J = 8.9, 1.9 Hz, 1H), 6.78 (d, J = 8.9 Hz, 1H), 4.31 (s, 1H), 4.20 (t, J = 5.0 Hz, 2H), 3.77 (t, J = 5.0 Hz, 2H), 2. 33 (d, J = 16.7 Hz, 1H), 1.65 (p, J = 8.0 Hz, 2H), 1.39-1.33 (m, 1H), 1.36-1.30 (m, 2H), 1.33-1.27 (m, 5H), 1.30-1.23 (m, 11H), 0.92-0.85 (m, 3H); the peak at 9.13 is the characteristic absorption peak of the imino group in the amide group.

[0047] Example 1

[0048] A photoresist developer is composed of the following raw materials in percentage by mass: 1% tetraethylammonium hydroxide, 0.2% diethylamine, 1% crown ether surfactant, 0.25% imidazole surfactant, 0.5% corrosion inhibitor, 0.15% accelerator, and the balance is water;

[0049] Among them, the crown ether type surfactant is prepared by Preparation Example 1; the imidazole type surfactant is 1-dodecyl-3-methyl-imidazolium bromide; the corrosion inhibitor is benzotriazole; and the accelerator is cinnamic acid.

[0050] Example 2

[0051] A photoresist developer is composed of the following raw materials in percentage by mass: 0.5% tetraethylammonium hydroxide, 0.5% diethylamine, 1.5% crown ether surfactant, 0.5% imidazole surfactant, 2% corrosion inhibitor, 0.05% accelerator, and the balance is water;

[0052] The crown ether surfactant is prepared in Preparation Example 1; the imidazole surfactant is 1-hexadecyl-3-methyl-imidazolium chloride; the corrosion inhibitor is 5-aminotetrazolyl; and the accelerator is caffeic acid.

[0053] Example 3

[0054] A photoresist developer is composed of the following raw materials in percentage by mass: 1.5% tetraethylammonium hydroxide, 0.1% diethylamine, 2% crown ether surfactant, 0.5% imidazole surfactant, 0.1% corrosion inhibitor, 0.5% accelerator, and the balance is water;

[0055] Among them, the crown ether type surfactant is prepared by Preparation Example 2; the imidazole type surfactant is obtained by mixing 1-dodecyl-3-methyl-imidazolium bromide and 1-hexadecyl-3-methyl-imidazolium chloride in a mass ratio of 1:1; the corrosion inhibitor is N-(3-aminopropyl)morpholine; and the accelerator is phenylalanine.

[0056] Example 4

[0057] A photoresist developer is composed of the following raw materials in percentage by mass: 1% tetraethylammonium hydroxide, 0.2% diethylamine, 1% crown ether surfactant, 0.25% imidazole surfactant, 0.5% corrosion inhibitor, 0.15% accelerator, and the balance is water;

[0058] Among them, the crown ether type surfactant is prepared by Preparation Example 1; the imidazole type surfactant is 1-hexadecyl-3-methyl-imidazole chloride; the corrosion inhibitor is benzotriazole; and the accelerator is cinnamic acid.

[0059] Example 5

[0060] A photoresist developer is composed of the following raw materials in percentage by mass: 1% tetraethylammonium hydroxide, 0.2% diethylamine, 1% crown ether surfactant, 0.25% imidazole surfactant, 0.5% corrosion inhibitor, 0.15% accelerator, and the balance is water;

[0061] Among them, the crown ether type surfactant is prepared by Preparation Example 1; the imidazole type surfactant is obtained by mixing 1-dodecyl-3-methyl-imidazolium bromide and 1-hexadecyl-3-methyl-imidazolium chloride in a mass ratio of 5:4; the corrosion inhibitor is benzotriazole; and the accelerator is cinnamic acid.

[0062] Comparative Example 1

[0063] Comparative Example 1 is different from Example 1 only in that the crown ether surfactant is replaced by an equal mass of dibenzo-18-crown-6-ether, as follows:

[0064] A photoresist developer is composed of the following raw materials in percentage by mass: 1% tetraethylammonium hydroxide, 0.2% diethylamine, 1% dibenzo-18-crown-6-ether, 0.25% imidazole surfactant, 0.5% corrosion inhibitor, 0.15% accelerator, and the balance is water;

[0065] Among them, the imidazole surfactant is 1-dodecyl-3-methyl-imidazolium bromide; the corrosion inhibitor is benzotriazole; and the accelerator is cinnamic acid.

[0066] Comparative Example 2

[0067] Comparative Example 2 is different from Example 1 only in that an equal mass of 4,7-dimethyl-5-decyne-4,7-diol is used to replace the crown ether surfactant, as follows:

[0068] A photoresist developer is composed of the following raw materials in percentage by mass: 1% tetraethylammonium hydroxide, 0.2% diethylamine, 1% 4,7-dimethyl-5-decyne-4,7-diol, 0.25% imidazole surfactant, 0.5% corrosion inhibitor, 0.15% accelerator, and the balance is water;

[0069] Among them, the imidazole surfactant is 1-dodecyl-3-methyl-imidazolium bromide; the corrosion inhibitor is benzotriazole; and the accelerator is cinnamic acid.

[0070] Comparative Example 3

[0071] Comparative Example 3 is different from Example 1 only in that an equal amount of crown ether surfactant is used to replace the imidazole surfactant, as follows:

[0072] A photoresist developer is composed of the following raw materials in percentage by mass: 1% tetraethylammonium hydroxide, 0.2% diethylamine, 1.25% crown ether surfactant, 0.5% corrosion inhibitor, 0.15% accelerator, and the balance is water;

[0073] Wherein, the crown ether type surfactant is prepared by Preparation Example 1; the corrosion inhibitor is benzotriazole; and the accelerator is cinnamic acid.

[0074] Comparative Example 4

[0075] Comparative Example 4 is different from Example 1 only in that an equal amount of imidazole-type surfactant is used to replace the crown ether-type surfactant, as follows:

[0076] A photoresist developer is composed of the following raw materials in percentage by mass: 1% tetraethylammonium hydroxide, 0.2% diethylamine, 1.25% imidazole surfactant, 0.5% corrosion inhibitor, 0.15% accelerator, and the balance is water;

[0077] Among them, the imidazole surfactant is 1-dodecyl-3-methyl-imidazolium bromide; the corrosion inhibitor is benzotriazole; and the accelerator is cinnamic acid.

[0078] Performance Testing

[0079] (1) Surface properties of developer

[0080] Dynamic surface tension: The dynamic surface tension of the developer obtained in Examples 1-5 and Comparative Examples 1-4 was measured by the maximum bubble pressure method, the capillary radius was 0.237 mm, the temperature was 25±0.1° C., the bubble surface life range was 10-50000 ms, and the dynamic tension curve was obtained; the following dynamic tension values ​​were taken when the bubble frequency was 6 Hz and the bubble life time was set to 100 ms; the results are shown in Table 1 below;

[0081] Contact angle: The photoresist was evenly spread on a smooth and clean glass surface by spin coating, and the excess solvent in the photoresist was extracted in a vacuum drying oven, and then the photoresist was completely dried in an oven at a temperature of 110° C. to prepare a sample to be tested; the contact angle between the developer obtained in Examples 1-5 and Comparative Examples 1-4 and the photoresist surface of the sample to be tested and the air was measured by the contact angle method; the test droplet volume was 5 μL, and the liquid was measured after 3 seconds of dropwise addition, and the test temperature was controlled at 23±0.5° C.; the results are shown in Table 1 below;

[0082] Foaming property: Take 20 mL of the developer obtained in Example 1 to Example 5 and Comparative Example 1 to Comparative Example 4, add it to a 100 mL measuring cylinder, vertically oscillate 30 times within 15 seconds, measure the foam height after standing for 15 minutes, repeat the measurement three times, record the foam height in mL, and take the average value; the results are shown in Table 1 below.

[0083] Table 1

[0084] Dynamic surface tension / (mN / m) Contact angle / ° Foam height / mL Example 1 28.8 30.27 25.7 Example 2 26.4 29.11 23.5 Example 3 27.3 29.65 24.9 Example 4 28.0 31.01 25.2 Example 5 25.3 27.53 23.6 Comparative Example 1 39.4 44.56 30.2 Comparative Example 2 33.1 35.45 26.3 Comparative Example 3 36.2 40.31 28.5 Comparative Example 4 44.5 50.32 35.4

[0085] It can be seen from Table 1 that the developer provided by the present invention has a low dynamic surface tension, can quickly reduce the contact angle during dynamic use, generates few bubbles and quickly defoams, and the crown ether surfactant and the imidazole surfactant interact with each other to achieve a wetting effect of 1+1>2.

[0086] (2) Development performance of developer

[0087] At 23°C, the developer obtained in Examples 1-5 and Comparative Examples 1-4 was diluted to 2.10 ms / cm, and the positive photoresist film required for the test was baked and exposed at 40 mj / cm 2 Expose the glass substrate with photoresist and place it on a developer to develop the photolithography pattern on the glass substrate; observe under a microscope: 1. Whether the developed pattern is clear; 2. Whether there is any photoresist residue; 3. Whether there is any substrate corrosion; 4. Whether the line width CD value (line width standard 10.0μm) is qualified: ○: CD error <0.5μm; ×: CD error ≥0.5μm; 5. Whether there is tailing phenomenon at the taper angle; The specific situation is shown in Table 2 below.

[0088] Table 2

[0089]

[0090]

[0091] The photoresist test piece treated with the developer obtained in Example 1 was characterized by scanning electron microscopy (SEM). The SEM image obtained by the characterization is as follows: Figure 3 As shown; the optical microscope image of the photoresist test piece after developer treatment is as shown Figure 4 As shown, Figure 3 and Figure 4 It can be seen that the developer has complete lines in photoresist development, no photoresist residue, no burrs, moderate angles, and no tailing;

[0092] The photoresist test piece treated with the developer obtained in Comparative Example 4 was characterized by scanning electron microscopy (SEM). The SEM image obtained by the characterization is as follows: Figure 5 As shown; the optical microscope image of the photoresist test piece after developer treatment is as shown Figure 6 As shown, Figure 5 and Figure 6 It can be seen that the developer has rough lines and tailing problems during photoresist development.

[0093] In addition, the developer obtained in Comparative Example 4 does not contain the crown ether surfactant of the present invention, which will cause certain corrosion to the substrate, which fully demonstrates that the crown ether surfactant of the present invention works together with other components to effectively improve the corrosion condition of the substrate; the crown ether surfactant can form a stable complex with metal ions, change the electrical and chemical properties of the substrate surface, and prevent corrosion of the substrate.

[0094] It should be noted that, in this article, relational terms such as first and second, etc. are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Moreover, the terms "include", "comprise" or any other variants thereof are intended to cover non-exclusive inclusion, so that a process, method, article or device including a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process, method, article or device.

[0095] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A crown ether surfactant, characterized in that The chemical structural formula of the crown ether type surfactant is as follows: In the formula, x is an integer from 1 to 3; y is an integer from 1 to 3; and m is an integer from 5 to 15.

2. A crown ether surfactant according to claim 1, characterized in that, x is 2, y is 2, and m is 10; Or, x is 1, y is 2, and m is 12.

3. A method for preparing a crown ether type surfactant as claimed in claim 1 or 2, characterized in that: The following steps are involved: Add diaminodibenzocrown ether, alkyl carboxylic acid and carboxyl activator into an organic solvent in a molar ratio of 1:2-2.5:2.2-3, mix well, and react at a constant temperature of 55-70°C for 4-7 hours. After the reaction is completed, filter, remove part of the solvent by rotary evaporation, and then purify by column chromatography, remove the eluent by rotary evaporation to obtain a crown ether type surfactant.

4. The method for preparing a crown ether type surfactant according to claim 3, characterized in that: The diaminodibenzo crown ether is one of diaminodibenzo-14-crown ether-4, diaminodibenzo-15-crown ether-5 and diaminodibenzo-18-crown ether-6.

5. The method for preparing a crown ether type surfactant according to claim 3, characterized in that: The alkyl carboxylic acid is one of hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid and hexadecanoic acid.

6. A photoresist developer, characterized in that: The invention is composed of the following raw materials in percentage by mass: 0.5%-1.5% of tetraethylammonium hydroxide, 0.1%-0.5% of diethylamine, 0.5%-2% of the crown ether surfactant described in any one of claims 1 to 2 or the crown ether surfactant prepared by the preparation method described in any one of claims 3 to 5, 0.1%-0.5% of imidazole surfactant, 0.1%-2% of corrosion inhibitor, 0.05%-0.5% of accelerator, and the balance is water.

7. A photoresist developer according to claim 6, characterized in that: The mass ratio of the crown ether surfactant to the imidazole surfactant is 2-4:

1.

8. A photoresist developer according to claim 6, characterized in that: The imidazole surfactant is 1-dodecyl-3-methyl-imidazolium bromide and / or 1-hexadecyl-3-methyl-imidazolium chloride.

9. A photoresist developer according to claim 8, characterized in that: The imidazole surfactant is obtained by mixing 1-dodecyl-3-methyl-imidazolium bromide and 1-hexadecyl-3-methyl-imidazolium chloride in a mass ratio of 5:2-5.

10. A photoresist developer according to claim 6, characterized in that: The corrosion inhibitor is one or more of benzotriazole, methimazole, N-(3-aminopropyl)morpholine, 5-aminotetrazolyl, 2,4-dihydroxypyrimidine and hydroxylated naphthoquinone; The accelerator is one or more of cinnamic acid, caffeic acid and phenylalanine.

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