A developer and use thereof

Abstract

This invention relates to G03F7, and more specifically, to a developer and its application. The developer comprises an organic base, an inorganic salt, a nonionic surfactant, and water. The developer provided by this invention offers fast development time, excellent development effect, does not damage the substrate, does not affect the patterned area of ​​the product, and is environmentally friendly and easy to process. The developer provided by this invention is particularly suitable for developing photoresists on glass, metal, silicon wafers, semiconductors, metal sensors, metal thin-film transistors, Metal OLEDs, Metal LCDs, and other similar materials.

Description

Technical Field

[0001] This invention relates to G03F7, and more specifically, to a developer and its application. Background Technology

[0002] Developer is an important solvent in the field of electrochemistry, used to dissolve the soluble areas of photoresist after exposure.

[0003] Patent CN101657761B provides a photoresist developer that incorporates anionic surfactants with a total sodium and potassium ion concentration of less than 10 ppm to prevent slagging in photoresist layers thicker than 3 μm. Patent CN107357140B provides a positive photoresist developer and its application, incorporating sodium polyhydroxycarboxylate as a metal protectant to reduce photoresist residue.

[0004] It is evident that the quality of the developer has a significant impact on the quality of electronic products. However, existing technologies often focus on the photoresist itself, investigating the amount of scum produced and the amount of residual photoresist, without exploring the impact of the amount of foam generated during cleaning on the stability of the cleaning process, or its effect on the developed pattern. Summary of the Invention

[0005] To address the aforementioned problems, the first aspect of this invention provides a developing solution, the raw materials of which include an organic base, an inorganic salt, a nonionic surfactant, and water.

[0006] Preferably, the raw materials of the developer include 0.8-1.1 parts by weight of organic base, 0.3-0.5 parts by weight of inorganic salt, 0.5-0.6 parts by weight of nonionic surfactant and 97.8-98.4 parts by weight of water.

[0007] In a preferred embodiment of the present invention, the organic base is a quaternary ammonium base.

[0008] As a preferred embodiment of the present invention, the quaternary ammonium base is selected from one or more of tetramethylammonium hydroxide, 2-hydroxy-N,N,N-trimethylethylammonium, and methyltriethylammonium hydroxide.

[0009] Preferably, the quaternary ammonium base is tetramethylammonium hydroxide.

[0010] As a preferred embodiment of the present invention, the inorganic salt is selected from one or more of sodium carbonate, potassium borate, potassium carbonate, and sodium silicate.

[0011] As a preferred embodiment of the present invention, the inorganic salt includes sodium carbonate and potassium borate, wherein the weight ratio of sodium carbonate to potassium borate in the inorganic salt is (0.05-0.2):(0.2-0.5).

[0012] More preferably, in the inorganic salt, the weight ratio of sodium carbonate to potassium borate is (0.05-0.2):0.3.

[0013] More preferably, the weight ratio of sodium carbonate to potassium borate in the inorganic salt is 0.1:0.3.

[0014] In a preferred embodiment of the present invention, the sodium carbonate is light sodium carbonate and / or heavy sodium carbonate.

[0015] Preferably, the sodium carbonate is heavy sodium carbonate.

[0016] By adding heavy sodium carbonate and controlling the weight ratio of sodium carbonate to potassium borate at (0.05-0.2):(0.2-0.5), the amount of tetramethylammonium hydroxide used is reduced while ensuring good developing results. This makes the developing solution more environmentally friendly and also reduces mobile ion contamination (MIC) caused by the high reactivity of metal ions, thus maintaining the operational stability of semiconductor devices. This is likely because the denser crystal structure of heavy sodium carbonate, with its extremely small intermolecular gaps, restricts the migration of metal ions when reacting with tetramethylammonium hydroxide and potassium borate. This limited intermolecular space restricts the movement of metal ions while maintaining good bonding between substances in the system, promoting the effect of tetramethylammonium hydroxide. Therefore, while ensuring good developing results, the amount of tetramethylammonium hydroxide used is reduced, and the damage to semiconductor devices caused by MIC is mitigated.

[0017] As a preferred embodiment of the present invention, the nonionic surfactant includes amide-based nonionic surfactants and ether-based nonionic surfactants.

[0018] Preferably, in the nonionic surfactant, the weight ratio of amide nonionic surfactant to ether nonionic surfactant is (0.13-0.2):(0.25-0.4).

[0019] More preferably, the weight ratio of amide-based nonionic surfactants to ether-based nonionic surfactants in the nonionic surfactants is 0.17:0.37.

[0020] As a preferred embodiment of the present invention, the amine value of the amide nonionic surfactant is 16-18.5 mgKOH / g.

[0021] Preferably, the amide-based nonionic surfactant is coconut oil fatty acid monoethanolamide.

[0022] As a preferred embodiment of the present invention, the HLB value of the ether-based nonionic surfactant is 10-20.

[0023] Preferably, the ether-based nonionic surfactant is tristyrylphenol polyoxyethylene ether.

[0024] When the developer is applied to the photoresist for development, an H2O reaction occurs between the developer and the photoresist. + Ion migration. Photoresists not only have large molecular weights but are also hydrophobic, making them difficult to dissolve in the developer, resulting in poor development quality. To address this issue, the applicant added an ether-based nonionic surfactant with an HLB value of 10-20 to the developer system to improve hydrophilicity. However, the applicant found that higher hydrophilicity of the added ether-based nonionic surfactant is not always better. Both excessively high and low HLB values ​​of the ether-based nonionic surfactant increase foam generation during development and cleaning, and also negatively impact the storage stability of the developer. Through extensive experimentation, the applicant discovered that adding 0.5-0.6 parts by weight of a nonionic surfactant to the system, along with an amide-based nonionic surfactant with an amine value of 16-18.5 mg KOH / g and an ether-based nonionic surfactant with an HLB value of 10-20, not only improves hydrophilicity but also enhances the stability of the developer and reduces foam generation during storage and cleaning. Especially when the weight ratio of amide nonionic surfactants to ether nonionic surfactants is (0.13-0.2):(0.25-0.4), it unexpectedly reduces the jaggedness of the pattern after development.

[0025] Preferably, the preparation process of the developer is as follows: mix all raw materials and stir for 3-5 hours to obtain the solution.

[0026] A second aspect of the present invention provides an application of a developer solution, which is used in the development process of semiconductor photoresist.

[0027] Compared with the prior art, the present invention has the following advantages:

[0028] The synergistic effect of 0.8-1.1 parts by weight of organic base, 0.3-0.5 parts by weight of inorganic salt, and 0.5-0.6 parts by weight of nonionic surfactant extends the shelf life of the developer. The addition of heavy sodium carbonate, with the weight ratio of sodium carbonate to potassium borate controlled at (0.05-0.2):(0.2-0.5), reduces the amount of tetramethylammonium hydroxide used while maintaining the developing effect, making the developer more environmentally friendly. It also reduces mobile ionic contamination (MIC) caused by the high activity of metal ions, maintaining the operational stability of semiconductor devices and minimizing its impact on voltage thresholds. Furthermore, the addition of 0.5-0.6 parts by weight of nonionic surfactant, along with the synergistic effect of amide nonionic surfactants with an amine value of 16-18.5 mg KOH / g and ether nonionic surfactants with an HLB value of 10-20, not only improves hydrophilicity but also enhances the stability of the developer, reducing foam generation during storage and cleaning. The developer provided by this invention offers fast development time, excellent development effect, no damage to the substrate, no impact on the product's patterned area, and is environmentally friendly and easy to process. This developer is particularly suitable for developing photoresists on glass, metal, silicon wafers, semiconductors, metal sensors, metal thin-film transistors, Metal OLEDs, Metal LCDs, and other similar materials. Detailed Implementation

[0029] Example

[0030] The raw materials used in the preparation of the compositions in the examples were all commercially available. The heavy soda ash was purchased from Shandong Weifang Haihua, the coconut oil fatty acid monoethanolamide was purchased from Zanyu with an amine value of 17.6 mg KOH / g, and the tristyrylphenol polyoxyethylene ether was purchased from Jiateng Chemical, model 601 with an HLB value of 12-16.

[0031] Example 1

[0032] This example provides a developer solution, the raw materials of which include 0.9 parts by weight of organic base, 0.4 parts by weight of inorganic salt, 0.54 parts by weight of nonionic surfactant and 98.16 parts by weight of water.

[0033] The organic base is a quaternary ammonium base. The quaternary ammonium base is tetramethylammonium hydroxide.

[0034] The inorganic salts include sodium carbonate and potassium borate, wherein the weight ratio of sodium carbonate to potassium borate is 0.1:0.3. The sodium carbonate is heavy sodium carbonate.

[0035] Nonionic surfactants include amide nonionic surfactants and ether nonionic surfactants.

[0036] In nonionic surfactants, the weight ratio of amide nonionic surfactants to ether nonionic surfactants is 0.17:0.37.

[0037] The amide-based nonionic surfactant is coconut oil fatty acid monoethanolamide. The ether-based nonionic surfactant is tristyrylphenol polyoxyethylene ether.

[0038] The preparation process of the developer is as follows: mix all raw materials and stir for 4 hours to obtain the solution.

[0039] Example 2

[0040] This example provides a developer solution that differs from Example 1 in that the raw materials of the developer solution include 1 part by weight of organic base, 0.45 parts by weight of inorganic salt, 0.6 parts by weight of nonionic surfactant, and 97.95 parts by weight of water.

[0041] Example 3

[0042] This example provides a developer solution that differs from Example 1 in that the raw materials of the developer solution include 0.8 parts by weight of organic base, 0.3 parts by weight of inorganic salt, 0.5 parts by weight of nonionic surfactant and 98.4 parts by weight of water.

[0043] Example 4

[0044] This example provides a developer solution that differs from Example 1 in that the raw materials of the developer solution include 1 part by weight of organic base, 0.5 parts by weight of inorganic salt, 0.6 parts by weight of nonionic surfactant and 97.9 parts by weight of water.

[0045] Inorganic salts include sodium carbonate and potassium carbonate, with a weight ratio of sodium carbonate to potassium carbonate of 0.15:0.35.

[0046] Example 5

[0047] This example provides a developer solution that differs from Example 1 in that the raw materials of the developer solution include 1.1 parts by weight of organic base, 0.4 parts by weight of inorganic salt, 0.55 parts by weight of nonionic surfactant, and 97.95 parts by weight of water. The nonionic surfactant is coconut oil fatty acid monoethanolamide.

[0048] Performance testing:

[0049] 1. Physicochemical tests: The physicochemical properties of the developer obtained in Example 1 were tested, and the results are shown in Table 1:

[0050] Table 1

[0051] Appearance transparent liquid proportion 1.16g / ml pH value 13 Flammability non-flammable

[0052] 2. Appearance Test: Electronic devices with a photoresist film thickness of 10μm (from Hunan Fanxin Technology Co., Ltd.) were immersed in 200mL of the developing solution obtained in Examples 1-5 and cleaned at 30℃. The cleaning time was set to 50s, 60s, and 70s respectively. The foaming situation, whether there were jagged edges in the developed pattern, and whether the developed pattern was complete were observed. The results are shown in Table 2.

[0053] Table 2

[0054]

[0055] 3. Stability Test: 20 mL of the developer obtained in Examples 1-5 was placed in a 50 mL test tube and kept at 40°C for 10 months. The presence of precipitation in the developer was observed after 6 and 10 months. The results are shown in Table 3.

[0056] Table 3

[0057]

[0058]

Claims

1. A developer, characterized in that, The raw materials for the developer include 0.8-1.1 parts by weight of organic base, 0.3-0.5 parts by weight of inorganic salt, 0.5-0.6 parts by weight of nonionic surfactant and 97.8-98.4 parts by weight of water; The organic base is a quaternary ammonium base, and the quaternary ammonium base is tetramethylammonium hydroxide; The inorganic salt includes sodium carbonate and potassium borate, wherein the weight ratio of sodium carbonate to potassium borate is (0.05-0.2):(0.2-0.5); the sodium carbonate is heavy sodium carbonate. The nonionic surfactants include amide nonionic surfactants and ether nonionic surfactants in a weight ratio of (0.13-0.2):(0.25-0.4). The amine value of the amide nonionic surfactant is 16-18.5 mgKOH / g; the amide nonionic surfactant is coconut oil fatty acid monoethanolamide; The ether-based nonionic surfactant has an HLB value of 10-20; the ether-based nonionic surfactant is tristyrylphenol polyoxyethylene ether.

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