阅读说明：本技术 一种具有高黏附性的ArF光刻胶树脂及其制备方法 (ArF photoresist resin with high adhesiveness and preparation method thereof ) 是由 马潇 陈鹏 樊丹 周浩杰 毛智彪 许从应 于 2019-10-09 设计创作，主要内容包括：本发明适用于电路制造材料技术领域,提供了一种具有高黏附性的ArF光刻胶树脂及其制备方法。该ArF光刻胶树脂含有如下按重量百分比计的组分：10％～40％内酯单体、20％～60％酸保护单体、0％～25％非极性单体和0％～15％腈基单体。本发明引入腈基结构,可以增加树脂与基材表面的作用力,增加黏附性,且腈基与硅烷偶联剂不同,不会与基材表面分子形成化学键。因此,在显影过程中可轻松去除,不会产生残留。使用本发明的ArF光刻胶树脂制备的光刻胶具有优异的黏附性,曝光区内的光刻胶没有残留,减小了光刻图形缺陷,提升了产品良率,光刻图形没有出现倒胶和剥离现象。(The invention is suitable for the technical field of circuit manufacturing materials, and provides ArF photoresist resins with high adhesiveness and a preparation method thereof, wherein the ArF photoresist resins comprise, by weight, 10% -40% of lactone monomers, 20% -60% of acid protection monomers, 0% -25% of nonpolar monomers and 0% -15% of nitrile monomers.)

1, ArF photoresist resin with high adhesiveness, which is characterized in that the ArF photoresist resin comprises the following components, by weight, 10% -40% of lactone monomer, 20% -60% of acid protection monomer, 0% -25% of nonpolar monomer and 0% -15% of nitrile group monomer;

the nitrile monomer has the following structure:

wherein R is₃H or CH₃；R₉＝C_nH_2nN is an integer of 1 to 12; r₁₀＝C_nH_2nAnd n is an integer of 1 to 12.

2. The ArF photoresist resin according to claim 1, wherein the ArF photoresist resin comprises the following components in percentage by weight: 20 to 30 percent of lactone monomer, 30 to 50 percent of acid protection monomer, 5 to 15 percent of nonpolar monomer and 1 to 10 percent of nitrile monomer.

3. The ArF photoresist resin of claim 1 or 2, wherein the lactone monomer has the structure:

wherein: r₁＝C_nH_2nN is an integer of 1 to 5; r₂＝C_nH_2nN is an integer of 1 to 5; r₃H or CH₃，R₆＝C_nH_2nAnd n is an integer of 1 to 5.

4. The ArF photoresist resin of claim 1 or 2, wherein the acid protecting monomer has the following structure:

wherein R is₃H or CH₃；R₄＝C_nH_2n+1N is an integer of 1 to 10; r₅H or CH₃；R₈＝C_nH_2n+1And n is an integer of 1 to 10.

5. The ArF photoresist resin of claim 1 or 2, wherein the non-polar monomer has the following structure:

wherein R is₃H or CH₃；R₁₁＝C_nH_2n+1N is an integer of 1 to 10; r₁₂＝C_nH_2n+1And n is an integer of 1 to 10.

6. The method for preparing ArF photoresist resin according to claim 1 or 2, comprising the steps of:

(1) adding 10-40% of lactone monomer, 20-60% of acid protection monomer, 0-25% of nonpolar monomer and 0-15% of nitrile monomer into a reaction kettle filled with nitrogen, adding ethyl acetate into the reaction kettle, uniformly stirring, heating the reaction kettle to 77-79 ℃, dropwise adding a mixed solution of ethyl acetate and an initiator into the reaction kettle, reacting for 7 hours at 77-79 ℃, stopping the reaction, and cooling the reaction kettle to room temperature, wherein the percentages are weight percentages;

(2) adding th methanol into the reaction kettle cooled to room temperature in the step (1), leading out liquid in the reaction kettle after precipitation is carried out for 1h, and then adding second ethyl acetate into the reaction kettle until the precipitate is dissolved, wherein the weight ratio of the th methanol to the th ethyl acetate is 100: 1;

(3) and (3) adding a second methanol into the reaction kettle in the step (2), repeating the operation in the step (2) to obtain a solid precipitate, and placing the solid precipitate in vacuum for drying to obtain the ArF photoresist resin, wherein the weight of the th methanol is the same as that of the second methanol.

7. The method for preparing ArF photoresist resin according to claim 6, wherein in the step (1), the dropping time is less than or equal to 30min, and the mass ratio of the th ethyl acetate to the initiator is 5:1-8: 1.

8. The method for preparing ArF photoresist resin as claimed in claim 7, wherein in step (1), the mass ratio of the lactone monomer to the th ethyl acetate is (30-35) to (8-10), and the initiator is dibenzoyl peroxide.

9. The method of preparing ArF photoresist resin according to claim 6, wherein the number of repetitions in step (3) is 5.

10, photoresists prepared from ArF photoresist resins of claims 1 or 2.

Technical Field

The invention belongs to the technical field of circuit manufacturing materials, and particularly relates to ArF photoresist resins with high adhesiveness and a preparation method thereof.

Background

The ArF photoresist is composed of resin, a photosensitizer, an additive solvent and the like, the resin is a carrier of the photoresist performance, has important influence on the performances of the photoresist such as resolution, line edge roughness and the like, and the ArF photoresist is a mainstream photoresist used in the current advanced integrated circuit manufacturing process, has thinner lines and is easy to strip and fall off, so that the photoresist pattern is defective along with the continuous reduction of the processing line width.

Patent application CN1828418A discloses copolymer film-forming resins containing silane coupling agents and deep ultraviolet positive chemical amplification type photoresist prepared by using the film-forming resins and taking ArF laser as an exposure light source, which can improve the adhesion of the photoresist and a substrate and obtain better photoresist patterns by reducing the absorption of the film-forming resins to light waves in 193nm waveband and changing the copolymerization of each monomer, and patent application CN104965389A discloses positive photoresist formulas, wherein the photoresist prepared by the formulas has higher resolution and definite toughness, is suitable for the requirements of flexible FPD/TP production processes, and solves the problems of cracking of a photoresist film, easy breakage and defect of the patterns and the like of the photoresist patterns.

Both patent application CN1828418A and patent application CN104965389A use silane coupling agent, which will react with the surface of the substrate to form stable silicon-oxygen bonds, and in the exposed area, the silicon-oxygen bonds formed between the silane coupling agent and the surface of the substrate will increase the adhesion of the photoresist, and the effect is obvious. Therefore, the residue is inevitably generated on the surface of the base material in the developing process and cannot be removed, so that the photoetching pattern generates defects, and the product yield is influenced.

Patent application CN107942623A discloses methods for enhancing adhesion of developed photoresist, after the photoresist is developed, steps of cleaning and soaking of deionized water are added to a silicon wafer, good adhesion between the photoresist and the silicon wafer is guaranteed, the problem of photoresist peeling during high-dose injection is solved, and process latitude is improved.

Disclosure of Invention

The embodiment of the invention provides ArF photoresist resins with high adhesiveness, and aims to solve the technical problems that residues are inevitably generated on the surface of a base material in the developing process and cannot be removed, so that the photoetching pattern is defective, the product yield is influenced, and the like.

The embodiment of the invention is realized by that ArF photoresist resins with excellent performance comprise the following components by weight percent, 10-40% of lactone monomer, 20-60% of acid protection monomer, 0-25% of nonpolar monomer and 0-15% of nitrile group monomer;

the nitrile monomer has the following structure:

wherein R is₃H or CH₃；R₉＝C_nH_2nN is an integer of 1 to 12; r₁₀＝C_nH_2nAnd n is an integer of 1 to 12.

, the ArF photoresist resin comprises the following components, by weight, 20% -30% of a lactone monomer, 30% -50% of an acid protection monomer, 5% -15% of a nonpolar monomer and 1% -10% of a nitrile group monomer.

Further , the lactone monomer has the structure:

wherein: r₁＝C_nH_2nN is an integer of 1 to 5; r₂＝C_nH_2nN is an integer of 1 to 5; r₃H or CH₃，R₆＝C_nH_2nAnd n is an integer of 1 to 5.

Further , the acid protecting monomer has the following structure:

wherein R is₃H or CH₃；R₄＝C_nH_2n+1N is an integer of 1 to 10; r₅H or CH₃；R₈＝C_nH_2n+1And n is an integer of 1 to 10.

Further , the nonpolar monomer has the structure:

wherein R is₃H or CH₃；R₁₁＝C_nH_2n+1N is an integer of 1 to 10; r₁₂＝C_nH_2n+1N is an integer of 1 to 10。

The embodiment of the invention also provides a preparation method of the ArF photoresist resin, which comprises the following steps:

(1) adding 10-40% of lactone monomer, 20-60% of acid protection monomer, 0-25% of nonpolar monomer and 0-15% of nitrile monomer into a reaction kettle filled with nitrogen, adding ethyl acetate into the reaction kettle, uniformly stirring, heating the reaction kettle to 77-79 ℃, dropwise adding a mixed solution of ethyl acetate and an initiator into the reaction kettle, reacting for 7 hours at 77-79 ℃, stopping the reaction, and cooling the reaction kettle to room temperature, wherein the percentages are weight percentages;

(2) adding th methanol into the reaction kettle cooled to room temperature in the step (1), leading out liquid in the reaction kettle after precipitation is carried out for 1h, and then adding second ethyl acetate into the reaction kettle until the precipitate is dissolved, wherein the weight ratio of the th methanol to the th ethyl acetate is 100: 1;

(3) and (3) adding a second methanol into the reaction kettle in the step (2), repeating the operation in the step (2) to obtain a solid precipitate, and placing the solid precipitate in vacuum for drying to obtain the ArF photoresist resin, wherein the weight of the th methanol is the same as that of the second methanol.

Further , in step (1):

the dripping time is less than or equal to 30 min;

the mass ratio of the th ethyl acetate to the initiator is 5:1-8: 1.

The mass ratio of the lactone monomer to the th ethyl acetate is (30-35) to (8-10).

The initiator is dibenzoyl peroxide.

Further , the number of repetitions in step (3) is 5.

kinds of photoresist prepared from the ArF photoresist resin.

ArF photoresist resin prepared by the method is prepared into photoresist, and a photoetching pattern is obtained through baking, exposing, developing and drying processes, and the result proves that the photoetching pattern has good adhesion to a substrate and has no phenomena of glue falling and stripping.

The ArF photoresist resin disclosed by the invention is added with a nitrile group-containing monomer in the preparation process, and the nitrile group is of a strong polarity structure, so that the strong polarity structure and a non-polar structure are matched in the resin, the resolution of the photoresist can be simultaneously improved, the line edge roughness is reduced, the adhesion of the resin is improved, and the overall performance of the photoresist is improved. The introduction of the nitrile group structure can increase the acting force of the resin and the surface of the base material and increase the adhesiveness, and the nitrile group is different from the silane coupling agent and cannot form a chemical bond with the molecules on the surface of the base material. Therefore, the developer can be easily removed in the developing process without generating residue. Therefore, the photoresist prepared by the ArF photoresist resin has excellent adhesiveness, the photoresist in an exposure area is not remained, the defects of a photoetching pattern are reduced, the yield of the product is improved, the phenomena of glue pouring and stripping do not occur in the photoetching pattern, and the adhesiveness with a base material is good.

Drawings

FIG. 1 is a lithographic pattern of a photoresist provided in example 1 of the present invention;

FIG. 2 is a photo-lithographic pattern of a photoresist provided in example 2 of the present invention;

FIG. 3 is a lithographic pattern of a photoresist provided in accordance with a comparative example of the present invention.

Detailed Description

For purposes of making the objects, aspects and advantages of the present invention more apparent, the present invention will be described in detail below with reference to the accompanying drawings and examples.

The ArF photoresist resin disclosed by the invention is added with a nitrile group-containing monomer in the preparation process, and the nitrile group is of a strong polarity structure, so that the strong polarity structure and a non-polar structure are matched in the resin, the resolution of the photoresist can be simultaneously improved, the line edge roughness is reduced, the adhesion of the resin is improved, and the overall performance of the photoresist is improved. The introduction of the nitrile group structure can increase the acting force of the resin and the surface of the base material and increase the adhesiveness, and the nitrile group is different from the silane coupling agent and cannot form a chemical bond with the molecules on the surface of the base material. Therefore, the developer can be easily removed in the developing process without generating residue. Therefore, the photoresist prepared by the ArF photoresist resin has excellent adhesiveness, the photoresist in an exposure area is not remained, the defects of a photoetching pattern are reduced, the yield of the product is improved, the phenomena of glue pouring and stripping do not occur in the photoetching pattern, and the adhesiveness with a base material is good.