A corrosion-resistant anti-reflective coating composition and its preparation method and application

Abstract

The present invention relates to the field of photolithography and discloses a corrosion-resistant anti-reflective coating composition, its preparation method, and its application. The corrosion-resistant anti-reflective coating composition comprises the following components in parts by weight: 15-20 parts acrylic resin, 2-4 parts catalyst, 6-8 parts cross-linking agent, and 300-700 parts solvent. The cross-linking agent is a mixed etherified melamine resin, which comprises a first mixed etherified melamine resin and a second mixed etherified melamine resin. The etherifying agents for the first mixed etherified melamine resin are methanol and n-butanol, while those for the second mixed etherified melamine resin are methanol and isobutanol. This technical solution addresses the poor corrosion resistance of anti-reflective coatings in related technologies.

Description

Technical Field

[0001] The present invention relates to the field of photolithography technology, and in particular to a corrosion-resistant anti-reflective coating composition, a preparation method thereof, and an application thereof. Background Art

[0002] In actual photolithography applications, anti-reflective coatings often need to face complex chemical environments, such as various corrosive chemical reagents and developers. If the corrosion resistance of the anti-reflective coating is poor, the various corrosive chemical reagents used in the photolithography process will directly destroy the optical properties of the coating, reducing its anti-reflective effect and failing to effectively reduce light reflection, thereby affecting the propagation of light in the photolithography process.

[0003] To address the poor corrosion resistance of anti-reflective coatings, existing technologies primarily aim to improve their corrosion resistance by adjusting the coating's formulation. Some studies have attempted to increase the content of certain polymers in the coating to enhance its chemical stability and improve corrosion resistance, but these efforts have been less than ideal and have negatively impacted the coating's anti-reflective properties.

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

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

[0006] The technical solution of the present invention is as follows: The present invention provides a corrosion-resistant anti-reflective coating composition, comprising the following component raw materials in parts by weight: 15-20 parts of acrylic resin, 2-4 parts of catalyst, 6-8 parts of cross-linking agent, and 300-700 parts of solvent; the cross-linking 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 anti-reflective coating composition of the present invention, different etherifying agents impart unique molecular structures and reactivity to the resins. The small molecular structure of methanol makes the resin highly reactive and can quickly initiate a crosslinking reaction, while the long carbon chain structures of n-butanol and isobutanol can adjust the flexibility and steric hindrance of the crosslinked network. 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 2:2-3, the two resins facilitate the formation of a dense three-dimensional network structure during the crosslinking process, significantly improving the density of the coating and enhancing the corrosion resistance of the coating.

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

[0010] As a further technical solution, the molar ratio of methoxy to butoxy 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 crosslinker of the corrosion-resistant anti-reflective coating composition of the present invention, a molar ratio of methoxy to butoxy groups in the first mixed etherified melamine resin of 3:1 achieves an optimal balance between crosslinking reactivity and overall coating performance. Excessively high methoxy content reduces the flexibility of the coating's molecular chains after film formation, making the film susceptible to cracking when attacked by external corrosive media, thereby reducing its protective effect on the substrate and subsequently decreasing corrosion resistance. On the other hand, when the methoxy content is too low, the film lacks density, allowing corrosive media to easily penetrate the film, similarly failing to effectively protect against external corrosion. A molar ratio of methoxy to butoxy groups of 3:1 helps improve the coating's corrosion resistance.

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

[0013] In the corrosion-resistant anti-reflective coating composition of the present invention, when the catalyst uses p-toluenesulfonic acid and a butyl organic compound in a mass ratio of 2:1-2, the two catalysts exert a synergistic effect. The p-toluenesulfonic acid has strong acidity and can quickly activate the active groups in the cross-linking agent. In the early stage of coating, it promotes a rapid cross-linking reaction between the acrylic resin and the mixed etherified melamine resin with high catalytic efficiency, quickly forming the basic framework structure of the coating, and laying the foundation for subsequent uniform film formation. However, if only relying on p-toluenesulfonic acid, the excessively fast reaction rate will lead to local overreaction, affecting the uniformity of the film layer. In this case, the butyl organic compound, with its mild catalytic properties, can regulate the reaction rate, avoid local over-crosslinking caused by excessively fast reaction in the early stage, and make the cross-linking reaction proceed smoothly and continuously, so that the film layer grows uniformly in the plane direction and thickness direction, thereby improving the uniformity of the film thickness formed by the coating composition.

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

[0015] In the corrosion-resistant anti-reflective coating composition of the present invention, the butyl organic compound is composed of dibutyltin dilaurate and butylphosphonic acid in a mass ratio of 1:1.2-1.5. The two compounds work synergistically. Dibutyltin dilaurate has good catalytic activity, which enables the coating to react more fully during the film-forming process. Butylphosphonic acid can also improve the fluidity and wettability of the coating. The two compounds work synergistically. The dibutyltin dilaurate-catalyzed reaction, based on the good fluidity improved by butylphosphonic acid, can be more evenly distributed on the surface of the substrate to form a more uniform film structure. The good wettability brought by butylphosphonic acid helps dibutyltin dilaurate to more fully contact the reactive components in the coating, further improving the catalytic efficiency and promoting a more complete reaction, thereby further improving the uniformity of the film thickness formed by 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-anthracenecarboxylic acid.

[0017] As a further technical solution, the acrylic resin is an acrylic resin with a weight average molecular weight of 15,000 prepared by conventional method from 4-hydroxybutyl acrylate glycidyl ether, 4-hydroxybutyl acrylate and 9-anthracenecarboxylic acid in a molar ratio of 1:1:1.

[0018] The present invention also provides a method for preparing a corrosion-resistant anti-reflective coating composition, which is used to prepare the corrosion-resistant anti-reflective coating composition, comprising the following steps: adding acrylic resin, a catalyst, and a cross-linking agent to a solvent, mixing, and obtaining the corrosion-resistant anti-reflective coating composition.

[0019] The present invention also provides a corrosion-resistant anti-reflective coating composition or an application of a corrosion-resistant anti-reflective coating composition prepared by the method for preparing the corrosion-resistant anti-reflective coating composition in a photolithography process.

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

[0021] The working principle and beneficial effects of the present invention are:

[0022] In the prior art, when adding a crosslinking agent to a coating composition, the primary focus is on the type of crosslinking agent. For example, amino resins and isocyanates can be used. Unlike the prior art, the present invention focuses on the impact of the differences in properties of etherified modified melamine resins, resulting from different etherifying agents, on the crosslinking system. In the present invention, a crosslinking agent system comprising a first mixed etherified melamine resin and a second mixed etherified melamine resin, obtained by etherification modification with different etherifying agents, is employed. The synergistic effect of the two agents is exploited to promote a more complete and orderly crosslinking reaction, forming a dense and uniform three-dimensional network structure that effectively blocks the penetration and erosion of corrosive media and enhances the corrosion resistance of the coating. DETAILED DESCRIPTION

[0023] 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 embodiments described 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 making any creative efforts are within the scope of protection of the present invention.

[0024] In the following examples and comparative examples:

[0025] The first mixed etherified melamine resin: the molar ratio of methoxy to butoxy is 3:1, the model is R-758, purchased from Guangzhou Longdi Chemical Co., Ltd.;

[0026] The second mixed etherified melamine resin: model M-16, purchased from Shenzhen Unibet Technology Co., Ltd.;

[0027] The acrylic resin is an acrylic resin with a weight average molecular weight of 15,000, prepared by a conventional method from 4-hydroxybutyl acrylate glycidyl ether, 4-hydroxybutyl acrylate and 9-anthracenecarboxylic acid in a molar ratio of 1:1:1.

[0028] Example 1

[0029] 15 parts of acrylic resin, 2 parts of p-toluenesulfonic acid, and 6 parts of a crosslinking agent were added to 300 parts of propylene glycol methyl ether acetate, and the mixture was mixed at 90° C. for 4 hours to obtain a corrosion-resistant anti-reflective coating composition;

[0030] The cross-linking agent consists of a first mixed etherified melamine resin (the molar ratio of methoxy group to butoxy group is 3:1) and a second mixed etherified melamine resin in a mass ratio of 1:1.

[0031] Example 2

[0032] 18 parts of acrylic resin, 3 parts of p-toluenesulfonic acid, and 7 parts of a crosslinking agent were added to 500 parts of cyclopentanone, and the mixture was mixed at 90° C. for 4 hours to obtain a corrosion-resistant anti-reflective coating composition;

[0033] The cross-linking agent consists of a first mixed etherified melamine resin (the molar ratio of methoxy group to butoxy group is 3:1) and a second mixed etherified melamine resin in a mass ratio of 1:1.

[0034] Example 3

[0035] 20 parts of acrylic resin, 4 parts of p-toluenesulfonic acid, and 8 parts of a crosslinking agent were added to 700 parts of propylene glycol methyl ether, and mixed at 90° C. for 4 hours to obtain a corrosion-resistant anti-reflective coating composition;

[0036] The cross-linking agent consists of a first mixed etherified melamine resin (the molar ratio of methoxy group to butoxy group is 3:1) and a second mixed etherified melamine resin in a mass ratio of 1:1.

[0037] Example 4

[0038] Compared with Example 3, Example 4 is different in that the crosslinking agent consists of a first mixed etherified melamine resin (the molar ratio of methoxy group to butoxy group is 3:1) and a second mixed etherified melamine resin in a mass ratio of 2:3.

[0039] Example 5

[0040] Compared with Example 4, the difference of Example 5 is that the first mixed etherified melamine resin (the molar ratio of methoxy to butoxy is 3:1) is replaced by 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.

[0041] Example 6

[0042] Compared with Example 4, Example 6 is different in that the first mixed etherified melamine resin (the molar ratio of methoxy to butoxy is 3:1) is replaced by 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.

[0043] Example 7

[0044] Compared with Example 4, Example 7 is different in that p-toluenesulfonic acid is replaced by an equal amount of dibutyltin dilaurate.

[0045] Example 8

[0046] Compared with Example 4, Example 8 is different in that p-toluenesulfonic acid is replaced by p-toluenesulfonic acid and dibutyltin dilaurate in a mass ratio of 2:1.

[0047] Example 9

[0048] Compared with Example 4, Example 9 is different in that p-toluenesulfonic acid is replaced by p-toluenesulfonic acid and dibutyltin dilaurate in a mass ratio of 1:1.

[0049] Example 10

[0050] Compared with Example 9, Example 10 is different in that dibutyltin dilaurate is replaced by an equal amount of butylphosphonic acid.

[0051] Example 11

[0052] Compared with Example 9, Example 11 is different in that dibutyltin dilaurate is replaced by dibutyltin dilaurate and butylphosphonic acid in a mass ratio of 1:1.2.

[0053] Example 12

[0054] Compared with Example 9, Example 12 is different in that dibutyltin dilaurate is replaced by dibutyltin dilaurate and butylphosphonic acid in a mass ratio of 1:1.5.

[0055] Example 13

[0056] Compared with Example 12, Example 13 is different in that dibutyltin dilaurate is replaced by an equal amount of stannous octoate.

[0057] Example 14

[0058] Compared with Example 12, Example 14 is different in that dibutyltin dilaurate is replaced by an equal amount of octylphosphonic acid.

[0059] Comparative Example 1

[0060] Compared with Example 3, the difference in Comparative Example 1 is that the cross-linking agent is only the first mixed etherified melamine resin.

[0061] Comparative Example 2

[0062] Compared with Example 3, the difference in Comparative Example 2 is that the cross-linking agent is only the second mixed etherified melamine resin.

[0063] Comparative Example 3

[0064] Compared with Example 3, the difference of Comparative Example 3 is that the cross-linking agent is only butylated melamine resin, model number U-VAN280, purchased from Guangzhou Longdi Chemical Co., Ltd.

[0065] Comparative Example 4

[0066] Compared with Example 3, the difference of Comparative 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 butylated melamine resin (model U-VAN280, purchased from Guangzhou Longti Chemical Co., Ltd.) in a mass ratio of 1:1.

[0067] Experimental Example 1

[0068] The coating compositions prepared in Examples 1 to 6 and Comparative Examples 1 to 4 were spin-coated on the surface of a silicon wafer. After baking and cross-linking at 200°C for 120 seconds, the neutral salt spray resistance of the samples was tested according to the test method specified in GB / T 10125-2021 "Artificial Atmosphere Corrosion Test Salt Spray Test", and the time when blistering or cracking of the coating appeared was recorded.

[0069] The test results are shown in Table 1:

[0070] Table 1 Performance test results of the corrosion-resistant anti-reflective coating compositions prepared in Examples 1 to 6 and Comparative Examples 1 to 4

[0071]

[0072] It can be seen from Table 1 that when the cross-linking 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.

[0073] Experimental Example 2

[0074] The corrosion-resistant anti-reflective coating compositions prepared in Example 4 and Examples 7 to 14 were spin-coated on a silicon wafer surface, baked and cross-linked at 200°C for 120 seconds, and the film thickness uniformity of the coating surface was measured at 100 points.

[0075] Film thickness uniformity = (maximum film thickness - minimum film thickness) / (maximum film thickness + minimum film thickness) × 100%.

[0076] The test results are shown in Table 2:

[0077] Table 2 Performance test results of the corrosion-resistant anti-reflective coating compositions prepared in Examples 4 and 7 to 14

[0078]

[0079] As shown in Table 2, when the catalyst consists of p-toluenesulfonic acid and a butyl organic compound in a mass ratio of 2:1-2, and the butyl organic compound consists of dibutyltin dilaurate and butylphosphonic acid in a mass ratio of 1:1.2-1.5, the uniformity of the film thickness formed by the coating composition can be improved.

[0080] The above are only 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 should be included in the scope of protection of the present invention.

Claims

1. A corrosion-resistant anti-reflective coating composition, characterized in that: The invention comprises the following raw materials in parts by weight: 15-20 parts of acrylic resin, 2-4 parts of catalyst, 6-8 parts of cross-linking agent, and 300-700 parts of solvent; the cross-linking 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; The mass ratio of the first mixed etherified melamine resin to the second mixed etherified melamine resin is 2:2-3; The molar ratio of methoxy to butoxy of 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; The catalyst is composed of p-toluenesulfonic acid and a butyl organic compound in a mass ratio of 2:1-2; The butyl organic compound consists of dibutyltin dilaurate and butylphosphonic acid in a mass ratio of 1:1.2-1.

5.

2. The corrosion-resistant anti-reflective coating composition according to claim 1, characterized in that: The solvent includes one or more of propylene glycol methyl ether acetate, cyclopentanone, and propylene glycol methyl ether.

3. The corrosion-resistant anti-reflective 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-anthracenecarboxylic acid.

4. A method for preparing a corrosion-resistant anti-reflective coating composition, for preparing a corrosion-resistant anti-reflective coating composition according to any one of claims 1 to 3, characterized in that: The method comprises the following steps: adding acrylic resin, a catalyst and a cross-linking agent into a solvent, mixing the mixture and obtaining a corrosion-resistant anti-reflective coating composition.

5. Use of a corrosion-resistant anti-reflective coating composition prepared according to any one of claims 1 to 3 or the method for preparing a corrosion-resistant anti-reflective coating composition according to claim 4 in a photolithography process.

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