Corrosion-resistant anti-reflection coating composition as well as preparation method and application thereof

Abstract

The invention relates to the technical field of photoetching, and provides a corrosion-resistant anti-reflection coating composition as well as a preparation method and application thereof. The corrosion-resistant anti-reflection coating composition comprises the following raw materials in parts by weight: 15-20 parts of acrylic resin, 2-4 parts of a catalyst, 6-8 parts of a cross-linking agent and 300-700 parts of a solvent, the cross-linking agent is mixed etherified melamine resin, the mixed etherified melamine resin is composed of first mixed etherified melamine resin and second mixed etherified melamine resin, etherifying agents of the first mixed etherified melamine resin are methyl alcohol and n-butyl alcohol, and etherifying agents of the second mixed etherified melamine resin are methyl alcohol and isobutyl alcohol. According to the technical scheme, the problem of poor corrosion resistance of the anti-reflection coating in the prior art is solved.

Description

Technical Field

[0001] The present invention relates to the field of lithography technology. Specifically, it relates to a corrosion-resistant antireflection coating composition, a preparation method thereof, and an application thereof. Background Art

[0002] In actual lithography process applications, antireflection coatings often need to face complex chemical environments, such as various corrosive chemical reagents, developers, etc. If the corrosion resistance of the antireflection coating is poor, various corrosive chemical reagents used in the lithography process will directly damage the optical properties of the coating, reduce its antireflection effect, and cannot effectively reduce light reflection, thereby affecting the propagation of light in the lithography process.

[0003] In order to solve the problem of poor corrosion resistance of antireflection coatings, the prior art mainly improves its corrosion resistance by adjusting the coating formula. Some studies have tried to increase the content of certain polymers in the coating to enhance its chemical stability and achieve the effect of improving corrosion resistance, but the effect is not ideal and will have a negative impact on the antireflection performance of the coating.

[0004] Therefore, it is very necessary to propose an antireflection coating composition with good corrosion resistance. Summary of the Invention

[0005] The present invention proposes a corrosion-resistant antireflection coating composition, a preparation method thereof, and an application thereof, which solves the problem of poor corrosion resistance of antireflection coatings in related technologies.

[0006] The technical solution of the present invention is as follows: The present invention proposes a corrosion-resistant antireflection coating composition, which includes the following raw material components in parts by weight: 15 - 20 parts of acrylic resin, 2 - 4 parts of catalyst, 6 - 8 parts of crosslinking agent, and 300 - 700 parts of solvent; the crosslinking agent is a mixed etherified melamine resin, and the mixed etherified melamine resin is composed of a first mixed etherified melamine resin and a second mixed etherified melamine resin. The etherifying agent of the first mixed etherified melamine resin is methanol and n-butanol, and the etherifying agent of the second mixed etherified melamine resin is methanol and isobutanol.

[0007] As a further technical solution, the mass ratio of the first mixed etherified melamine resin to the second mixed etherified melamine resin is 2:2 - 3.

[0008] In the crosslinking agent of the corrosion-resistant and antireflective coating composition of the present invention, different etherifying agents endow the resin with unique molecular structures and reaction activities. The small molecular structure of methanol gives the resin high reaction activity and can rapidly initiate the crosslinking reaction, while the long carbon chain structures of n-butanol and isobutanol can adjust the flexibility and steric hindrance of the crosslinking network. When the two resins cooperate with each other, when the mass ratio of the first mixed etherified melamine resin to the second mixed etherified melamine resin is 2:2 to 3, it helps to form a dense three-dimensional network structure during the crosslinking process, significantly improving the denseness of the coating and enhancing the corrosion resistance of the coating.

[0009] As a further technical solution, the molar ratio of methoxy groups to butoxy groups in the first mixed etherified melamine resin is 1 to 9:1.

[0010] As a further technical solution, the molar ratio of methoxy groups to butoxy groups in the first mixed etherified melamine resin is 3:1, and the model is R-758. The model of the second mixed etherified melamine resin is M-16.

[0011] In the crosslinking agent of the corrosion-resistant and antireflective coating composition of the present invention, when the molar ratio of methoxy groups to butoxy groups in the first mixed etherified melamine resin is 3:1, an optimal balance can be achieved between the crosslinking reaction activity and the comprehensive performance of the coating. If the content of methoxy groups is too high, after the coating forms a film, the flexibility of the molecular chain decreases, and when it is eroded by external corrosive media, cracks are likely to occur in the film layer, thereby reducing the protective effect on the substrate and the corrosion resistance also decreases accordingly; while when the proportion of methoxy groups is too low, the denseness of the film layer is insufficient, and the corrosive media is easily permeated into the interior of the film layer, and it also cannot effectively resist external corrosion. When the molar ratio of methoxy groups to butoxy groups is 3:1, it helps to improve the corrosion resistance of the coating.

[0012] As a further technical solution, the catalyst is composed of p-toluenesulfonic acid and a butyl organic compound with a mass ratio of 2:1 to 2.

[0013] In the corrosion-resistant and antireflective coating composition of the present invention, when the catalyst is p-toluenesulfonic acid and butyl organic compound with a mass ratio of 2:1 to 2, the two catalysts exert a synergistic effect. p-Toluenesulfonic acid has strong acidity and can quickly activate the active groups in the crosslinking agent. In the initial stage of coating application, it can promote the rapid crosslinking reaction between the acrylic resin and the mixed etherified melamine resin with a high catalytic efficiency, quickly forming the basic framework structure of the coating, laying a foundation for subsequent uniform film formation. However, if relying solely on p-toluenesulfonic acid, the too-fast reaction rate will lead to excessive local reaction, affecting the film layer uniformity. At this time, the butyl organic compound, relying on its mild catalytic characteristics, can adjust the reaction rate, avoid the phenomenon of local over-crosslinking caused by the too-fast reaction in the early stage, enable the crosslinking reaction to proceed smoothly and continuously, and make the film layer grow uniformly in the planar direction and thickness direction, improving the film thickness uniformity of the coating composition formed.

[0014] As a further technical solution, the butyl organic compound is composed of dibutyltin dilaurate and butylphosphonic acid with a mass ratio of 1:1.2 to 1.5.

[0015] In the corrosion-resistant and antireflective coating composition of the present invention, the butyl organic compound is composed of dibutyltin dilaurate and butylphosphonic acid with a mass ratio of 1:1.2 to 1.5, and the two play a synergistic role. Dibutyltin dilaurate has good catalytic activity, making the reaction in the film-forming process of the coating more sufficient. Butylphosphonic acid can also improve the fluidity and wettability of the coating. The two work together. Based on the good fluidity improved by butylphosphonic acid, the catalytic reaction of dibutyltin dilaurate can be more evenly distributed on the substrate surface, forming a more uniform film layer structure. The good wettability brought by butylphosphonic acid helps dibutyltin dilaurate to more fully contact the reaction components in the coating, further improving the catalytic efficiency, promoting the reaction to be more complete, and thus further improving the film thickness uniformity of the coating composition.

[0016] As a further technical solution, the raw materials of the acrylic resin include 4-hydroxybutyl acrylate glycidyl ether, 4-hydroxybutyl acrylate, and 9-anthracene carboxylic acid.

[0017] As a further technical solution, the acrylic resin is an acrylic resin with a weight average molecular weight of 15000 prepared by 4-hydroxybutyl acrylate glycidyl ether, 4-hydroxybutyl acrylate, and 9-anthracene carboxylic acid in a molar ratio of 1:1:1 according to a conventional method.

[0018] The present invention also provides a preparation method of a corrosion-resistant and antireflective coating composition for preparing the corrosion-resistant and antireflective coating composition described above, including the following steps: adding an acrylic resin, a catalyst, and a crosslinking agent into a solvent, and mixing to obtain the corrosion-resistant and antireflective coating composition.

[0019] The present invention also provides an application of a corrosion-resistant and antireflective coating composition or a corrosion-resistant and antireflective coating composition prepared by the preparation method of the corrosion-resistant and antireflective coating composition in a lithography process.

[0020] As a further technical solution, the temperature of the mixing is 80-100 °C, for example, it can be 80 °C, 85 °C, 90 °C, 95 °C, 100 °C, preferably 90 °C, and the time is 3-4 h, for example, it can be 3 h, 3.2 h, 3.4 h, 3.6 h, 3.8 h, 4.0 h, preferably 4.0 h.

[0021] The working principle and beneficial effects of the present invention are as follows: In the prior art, when adding a crosslinking agent to a coating composition, the type of the crosslinking agent is mainly concerned. For example, amino resin types, isocyanate types, etc. Different from the prior art, in the present invention, the focus is on the influence of the characteristic differences of the etherified melamine resin brought by different etherifying agents on the crosslinking system. In the present invention, an etherified melamine resin obtained by etherification modification with different etherifying agents, that is, a crosslinking agent system composed of a first mixed etherified melamine resin and a second mixed etherified melamine resin, is used to exert the synergistic effect of the two, promote the crosslinking reaction to proceed more fully and orderly, form a dense and uniform three-dimensional network structure, effectively block the penetration and erosion of corrosive media, and improve the corrosion resistance of the coating. Detailed Embodiments

[0022] 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. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts fall within the scope of the present invention.

[0023] In the following examples and comparative examples: The first mixed etherified melamine resin: the molar ratio of methoxy to butoxy is 3:1, the model is R-758, and it is purchased from Guangzhou Longdi Chemical Co., Ltd.; The second mixed etherified melamine resin: the model is M-16, and it is purchased from Shenzhen Younibait Technology Co., Ltd.; The acrylic resin is an acrylic resin with a weight average molecular weight of 15000 prepared by a conventional method from 4-hydroxybutyl acrylate glycidyl ether, 4-hydroxybutyl acrylate and 9-anthracene carboxylic acid with a molar ratio of 1:1:1.

[0024] Example 1 Add 15 parts of acrylic resin, 2 parts of p-toluenesulfonic acid, and 6 parts of crosslinking agent to 300 parts of propylene glycol methyl ether acetate, and mix at 90 °C for 4 h to obtain a corrosion-resistant antireflection coating composition; The crosslinking agent is composed of a first mixed etherified melamine resin (the molar ratio of methoxy to butoxy is 3:1) and a second mixed etherified melamine resin with a mass ratio of 1:1.

[0025] Example 2 Add 18 parts of acrylic resin, 3 parts of p-toluenesulfonic acid, and 7 parts of crosslinking agent to 500 parts of cyclopentanone, and mix at 90 °C for 4 h to obtain a corrosion-resistant antireflection coating composition; The crosslinking agent is composed of a first mixed etherified melamine resin (the molar ratio of methoxy to butoxy is 3:1) and a second mixed etherified melamine resin with a mass ratio of 1:1.

[0026] Example 3 Add 20 parts of acrylic resin, 4 parts of p-toluenesulfonic acid, and 8 parts of crosslinking agent to 700 parts of propylene glycol methyl ether, and mix at 90 °C for 4 h to obtain a corrosion-resistant antireflection coating composition; The crosslinking agent is composed of a first mixed etherified melamine resin (the molar ratio of methoxy to butoxy is 3:1) and a second mixed etherified melamine resin with a mass ratio of 1:1.

[0027] Example 4 Compared with Example 3, the difference in Example 4 is that the crosslinking agent is composed of a first mixed etherified melamine resin (the molar ratio of methoxy to butoxy is 3:1) and a second mixed etherified melamine resin with a mass ratio of 2:3.

[0028] Example 5 Compared with Example 4, the difference in Example 5 is that the first mixed etherified melamine resin (the molar ratio of methoxy to butoxy is 3:1) is replaced with an equal amount of mixed etherified melamine resin (the molar ratio of methoxy to butoxy is 1:1), model CE-7103, purchased from Guangzhou Longdi Chemical Co., Ltd.

[0029] Example 6 Compared with Example 4, the difference in Example 6 is that the first mixed etherified melamine resin (the molar ratio of methoxy to butoxy is 3:1) is replaced with an equal amount of mixed etherified melamine resin (the molar ratio of methoxy to butoxy is 9:1), model Melamines IAMEL 5507, purchased from Guangzhou Hongshang Trading Co., Ltd.

[0030] Example 7 Compared with Example 4, the difference in Example 7 is that p-toluenesulfonic acid is replaced with an equal amount of dibutyltin dilaurate.

[0031] Example 8 Compared with Example 4, Example 8 is different in that p-toluenesulfonic acid is replaced with a mixture of p-toluenesulfonic acid and dibutyltin dilaurate with a mass ratio of 2:1.

[0032] Example 9 Compared with Example 4, Example 9 is different in that p-toluenesulfonic acid is replaced with a mixture of p-toluenesulfonic acid and dibutyltin dilaurate with a mass ratio of 1:1.

[0033] Example 10 Compared with Example 9, Example 10 is different in that dibutyltin dilaurate is replaced with an equal amount of butylphosphonic acid.

[0034] Example 11 Compared with Example 9, Example 11 is different in that dibutyltin dilaurate is replaced with a mixture of dibutyltin dilaurate and butylphosphonic acid with a mass ratio of 1:1.2.

[0035] Example 12 Compared with Example 9, Example 12 is different in that dibutyltin dilaurate is replaced with a mixture of dibutyltin dilaurate and butylphosphonic acid with a mass ratio of 1:1.5.

[0036] Example 13 Compared with Example 12, Example 13 is different in that dibutyltin dilaurate is replaced with an equal amount of stannous octoate.

[0037] Example 14 Compared with Example 12, Example 14 is different in that dibutyltin dilaurate is replaced with an equal amount of octylphosphonic acid.

[0038] Comparative Example 1 Compared with Example 3, Comparative Example 1 is different in that the crosslinking agent is only the first mixed etherified melamine resin.

[0039] Comparative Example 2 Compared with Example 3, Comparative Example 2 is different in that the crosslinking agent is only the second mixed etherified melamine resin.

[0040] Comparative Example 3 Compared with Example 3, Comparative Example 3 is different in that the crosslinking agent is only butyl etherified melamine resin, model U-VAN280, purchased from Guangzhou Longdi Chemical Co., Ltd.

[0041] Comparative Example 4 Compared with Example 3, the difference in Comparative Example 4 is that the crosslinking agent consists of a first mixed etherified melamine resin with a mass ratio of 1:1 (the molar ratio of methoxy to butoxy is 3:1) and a butyl etherified melamine resin (model U-VAN280, purchased from Guangzhou Longdi Chemical Co., Ltd.).

[0042] Experimental Example 1 The coating compositions prepared in Examples 1-6 and Comparative Examples 1-4 were spin-coated on the surface of silicon wafers. After baking and crosslinking at 200 °C for 120 seconds, according to the test method specified in GB / T 10125-2021 "Artificial Atmosphere Corrosion Test - Salt Spray Test", the neutral salt spray resistance of the samples was tested, and the time when the coating showed blistering or cracking was recorded.

[0043] The test results are shown in Table 1 as follows: Table 1 Performance test results of the corrosion-resistant and antireflective coating compositions prepared in Examples 1-6 and Comparative Examples 1-4

[0044] As can be seen from Table 1, when the crosslinking agent consists of the first mixed etherified melamine resin and the second mixed etherified melamine resin, the corrosion resistance of the coating can be improved.

[0045] Experimental Example 2 The corrosion-resistant and antireflective coating compositions prepared in Example 4 and Examples 7-14 were spin-coated on the surface of silicon wafers. After baking and crosslinking at 200 °C for 120 seconds, 100 points were taken to measure the film thickness uniformity on the surface of the coating; Film thickness uniformity = (maximum film thickness - minimum film thickness) / (maximum film thickness + minimum film thickness) × 100%.

[0046] The test results are shown in Table 2 as follows: Table 2 Performance test results of the corrosion-resistant and antireflective coating compositions prepared in Example 4 and Examples 7-14

[0047] As can be seen from Table 2, when the catalyst consists of p-toluenesulfonic acid and a butyl organic compound with a mass ratio of 2:1 to 2, and the butyl organic compound consists of dibutyltin dilaurate and butylphosphonic acid with a mass ratio of 1:1.2 to 1.5, the film thickness uniformity formed by the coating composition can be improved.

[0048] The above are only the preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention shall be included within the protection scope of the present invention.

Claims

1. A corrosion-resistant and antireflective coating composition, characterized in that, It comprises the following raw material components in parts by weight: 15 - 20 parts of acrylic resin, 2 - 4 parts of catalyst, 6 - 8 parts of crosslinking agent, and 300 - 700 parts of solvent; the crosslinking agent is a mixed etherified melamine resin, and the mixed etherified melamine resin is composed of a first mixed etherified melamine resin and a second mixed etherified melamine resin. The etherifying agent of the first mixed etherified melamine resin is methanol and n - butanol, and the etherifying agent of the second mixed etherified melamine resin is methanol and isobutanol.

2. The corrosion-resistant and antireflection coating composition according to claim 1, wherein The mass ratio of the first mixed etherified melamine resin to the second mixed etherified melamine resin is 2:2 - 3.

3. The corrosion-resistant and antireflective coating composition according to claim 2, wherein, The molar ratio of methoxy to butoxy in the first mixed etherified melamine resin is 1 - 9:

1.

4. The corrosion-resistant and antireflection coating composition according to claim 2, characterized in that, The molar ratio of methoxy to butoxy in the first mixed etherified melamine resin is 3:1, and its model is R - 758, and the model of the second mixed etherified melamine resin is M - 16.

5. The corrosion-resistant and antireflection coating composition according to claim 1, wherein The catalyst is composed of p - toluenesulfonic acid and a butyl organic compound with a mass ratio of 2:1 - 2.

6. The corrosion-resistant and antireflective coating composition according to claim 5, characterized in that, The butyl organic compound is composed of dibutyltin dilaurate and butylphosphonic acid with a mass ratio of 1:1.2 - 1.

5.

7. The corrosion-resistant and antireflective coating composition according to claim 1, wherein The solvent includes one or more of propylene glycol methyl ether acetate, cyclopentanone, and propylene glycol methyl ether.

8. The corrosion-resistant and antireflective coating composition according to claim 1, characterized in that The raw materials of the acrylic resin include 4 - hydroxybutyl acrylate glycidyl ether, 4 - hydroxybutyl acrylate, and 9 - anthracene carboxylic acid.

9. A method for preparing a corrosion-resistant and antireflective coating composition for preparing a corrosion-resistant and antireflective coating composition according to any one of claims 1 to 8, characterized in that, It includes the following steps: adding the acrylic resin, catalyst, and crosslinking agent into the solvent and mixing to obtain a corrosion - resistant and antireflective coating composition.

10. Application of a corrosion - resistant and antireflective coating composition prepared according to any one of claims 1 - 8 or the preparation method of the corrosion - resistant and antireflective coating composition according to claim 9 in a lithography process.

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