阅读说明：本技术 一种光刻胶树脂及其制备方法 (Photoresist resin and preparation method thereof ) 是由 顾大公 马潇 余绍山 陈鹏 齐国强 许东升 毛智彪 许从应 于 2020-12-31 设计创作，主要内容包括：本发明公开了一种光刻胶树脂及其制备方法,该方法包括：预处理：将至少两种丙烯酸酯类单体与有机溶剂在氮气环境下进行均匀混合,得到混合液,其中,所述丙烯酸酯类单体中极性单体与非极性单体的质量比为(3-7)：(3-7)；光刻胶树脂的合成：氮气环境下在所述混合液中加入引发剂并进行搅拌、升温反应,得到聚合物溶液；光刻胶树脂的分离提纯：在所述聚合物溶液中加入沉淀剂并进行抽滤干燥,得到光刻胶树脂。通过该方法制备得到的光刻胶树脂可以较好的调控树脂的极性组分与非极性组分,该光刻胶树脂在进行应用的过程中,使得光刻胶膜的显影液浸润性和光刻胶膜与衬底的黏附性适中,同时减少了光刻胶膜在显影液中的过多损失。(The invention discloses a photoresist resin and a preparation method thereof, wherein the method comprises the following steps: pretreatment: uniformly mixing at least two acrylate monomers and an organic solvent in a nitrogen environment to obtain a mixed solution, wherein the mass ratio of polar monomers to non-polar monomers in the acrylate monomers is (3-7): (3-7); synthesis of photoresist resin: adding an initiator into the mixed solution under a nitrogen environment, stirring, and heating for reaction to obtain a polymer solution; and (3) separation and purification of the photoresist resin: and adding a precipitator into the polymer solution, and performing suction filtration and drying to obtain the photoresist resin. The photoresist resin prepared by the method can well regulate and control the polar component and the non-polar component of the resin, and the photoresist resin has moderate developing solution wettability of a photoresist film and adhesiveness of the photoresist film and a substrate in the application process, and simultaneously reduces excessive loss of the photoresist film in the developing solution.)

1. A method for preparing a photoresist resin, comprising the steps of:

pretreatment: uniformly mixing at least two acrylate monomers and an organic solvent in a nitrogen environment to obtain a mixed solution, wherein the mass ratio of polar monomers to non-polar monomers in the acrylate monomers is (3-7): (3-7);

synthesis of photoresist resin: adding an initiator into the mixed solution under a nitrogen environment, stirring, and heating for reaction to obtain a polymer solution;

and (3) separation and purification of the photoresist resin: and adding a precipitator into the polymer solution, and performing suction filtration and drying to obtain the photoresist resin.

2. The method for preparing the photoresist resin according to claim 1, wherein the specific structural general formula of the nonpolar monomer in the acrylate monomers is:

wherein R is_aIs H or a carbon chain with 1-20 carbon atoms; r_bA functional group that is an acid sensitive quaternary carbon or polycyclic alkyl compound;

the specific structural general formula of the polar monomer in the acrylate monomer is as follows:

wherein R is_cIs H or a carbon chain with 1-20 carbon atoms; r_dIs a functional group of a polycyclic compound containing an ester bond or a hydroxyl group having strong polarity.

3. The method of claim 2, wherein R is the same as R_bWhen the functional group is acid-sensitive quaternary carbon, the carbon number is between 3 and 30, and all hydrogen atoms of carbon atoms connected with ester bond oxygen atoms are substituted by other groups to form one or more of tert-butyl ester, substituted tert-butyl ester, alkyl substituted adamantyl derivative ester, alkyl substituted norbornyl derivative ester, alkyl substituted cyclic alkyl ester and alkyl substituted cyclic alkyl derivative ester.

4. The method of claim 2, wherein R is the same as R_bIn the case of a functional group of a polycyclic alkyl compound, the number of carbon atoms is 3 to 30, and the hydrogen atom of the carbon atom bonded to the oxygen atom of the ester bond is not completely substituted with other groups to form a tert-butyl ester, a substituted tert-butyl ester, an alkyl-substituted adamantyl derivative ester, an alkyl-substituted norbomideOne or more of a platelet ester, an alkyl-substituted norbornyl derivative ester, an alkyl-substituted cyclic alkyl ester, and an alkyl-substituted cyclic alkyl derivative ester.

5. The method of claim 2, wherein R is selected from the group consisting of_dThe functional group is a functional group with 6-30 carbon atoms, contains a hydroxyl-containing cyclic, cage-shaped or straight-chain carbon-containing structure and various lactone structures, and has a structure of one or more of adamantane ester containing 1 or more independent hydroxyl groups, cyclohexyl ester containing 1 or more independent hydroxyl groups, cyclopentyl ester containing 1 or more independent hydroxyl groups, polycycle ester compound containing 1 or more independent hydroxyl groups, cage-shaped ester compound containing 1 or more independent hydroxyl groups, butyrolactone, valerolactone, substituted valerolactone, caprolactone, substituted caprolactone, lactone containing adamantane structure, lactone containing polycyclic structure and lactone containing cage-shaped structure.

6. The method as claimed in claim 1, wherein the concentration of water in the acrylate monomer is less than 100ppm, the purity of the acrylate monomer is higher than 90%, the molecular weight of the photoresist resin is 8000-10000, and the PDI distribution is less than 2.

7. The method of claim 1, wherein the organic solvent is one or more of methanol, ethanol, dioxane, acetone, methyl ethyl ketone, cyclohexanone, tetrahydrofuran, methyl tetrahydrofuran, benzene, toluene, xylene, chloroform, dichloroethane, and trichloroethane.

8. The method of claim 1, wherein the precipitating agent is one or more of pure water, methanol/water mixture, ethanol/water mixture, isopropanol/water mixture, n-heptane, n-hexane, cyclohexane, n-pentane, petroleum ether, diethyl ether, and methyl tert-butyl ether.

9. The method as claimed in claim 1, wherein the temperature-raising reaction is carried out under 50-90 ℃ and the stirring rate is 300-600R/min.

10. A photoresist resin characterized by being prepared by the method of any one of claims 1 to 9.

Technical Field

The invention relates to the technical field of photoresist, in particular to photoresist resin and a preparation method thereof.

Background

The polarity of the photoresist resin determines the developer wettability of the photoresist film and the adhesion of the photoresist film to the substrate. If the photoresist resin is too non-polar, the developing solution wettability of the photoresist film and the adhesiveness between the photoresist film and the substrate are poor, which easily causes the problems of line width roughness, sensitivity, photoresist falling, photoresist residue, etc.; if the resin is too polar, the immersion property of the developing solution of the photoresist film and the adhesion between the photoresist film and the substrate are too strong, so that the photoresist film is lost too much in the developing solution, and the residual photoresist film is not thick enough to meet the requirements of the etching process.

Disclosure of Invention

The embodiment of the invention provides a photoresist resin and a preparation method thereof, aiming at solving the problem that the prior art can not well regulate and control the polar component and the non-polar component of the photoresist resin, so that the etching process can not be satisfied.

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

pretreatment: uniformly mixing at least two acrylate monomers and an organic solvent in a nitrogen environment to obtain a mixed solution, wherein the mass ratio of polar monomers to non-polar monomers in the acrylate monomers is (3-7): (3-7);

synthesis of photoresist resin: adding an initiator into the mixed solution under a nitrogen environment, stirring, and heating for reaction to obtain a polymer solution;

and (3) separation and purification of the photoresist resin: and adding a precipitator into the polymer solution, and performing suction filtration and drying to obtain the photoresist resin.

Preferably, in the method for preparing the photoresist resin, the specific structural general formula of the nonpolar monomer in the acrylate monomers is:

wherein R is_aIs H or a carbon chain with 1-20 carbon atoms; r_bA functional group that is an acid sensitive quaternary carbon or polycyclic alkyl compound;

the specific structural general formula of the polar monomer in the acrylate monomer is as follows:

wherein R is_cIs H or a carbon chain with 1-20 carbon atoms; r_dIs a functional group of a polycyclic compound containing an ester bond or a hydroxyl group having strong polarity.

More preferably, in the method for preparing a photoresist resin, if R is_bWhen the functional group is acid-sensitive quaternary carbon, the carbon number is between 3 and 30, and all hydrogen atoms of carbon atoms connected with ester bond oxygen atoms are substituted by other groups to form one or more of tert-butyl ester, substituted tert-butyl ester, alkyl substituted adamantyl derivative ester, alkyl substituted norbornyl derivative ester, alkyl substituted cyclic alkyl ester and alkyl substituted cyclic alkyl derivative ester.

More preferably, in the method for preparing a photoresist resin, if R is_bIn the case of a functional group of a polycyclic alkyl compound, the number of carbon atoms is 3 to 30, and the hydrogen atom of the carbon atom bonded to the oxygen atom of the ester bond is not completely substituted with other groups, and forms one or more of tert-butyl ester, substituted tert-butyl ester, alkyl-substituted adamantyl derivative ester, alkyl-substituted norbornyl derivative ester, alkyl-substituted cyclic alkyl ester, and alkyl-substituted cyclic alkyl derivative ester。

More preferably, in the method for preparing a photoresist resin, the R is_dThe functional group is a functional group with 6-30 carbon atoms, contains a hydroxyl-containing cyclic, cage-shaped or straight-chain carbon-containing structure and various lactone structures, and has a structure of one or more of adamantane ester containing 1 or more independent hydroxyl groups, cyclohexyl ester containing 1 or more independent hydroxyl groups, cyclopentyl ester containing 1 or more independent hydroxyl groups, polycycle ester compound containing 1 or more independent hydroxyl groups, cage-shaped ester compound containing 1 or more independent hydroxyl groups, butyrolactone, valerolactone, substituted valerolactone, caprolactone, substituted caprolactone, lactone containing adamantane structure, lactone containing polycyclic structure and lactone containing cage-shaped structure.

Preferably, in the preparation method of the photoresist resin, the concentration of water in the acrylate monomer is lower than 100ppm, the purity of the acrylate monomer is higher than 90%, the molecular weight of the photoresist resin is 8000-10000, and the PDI distribution is less than 2.

Preferably, in the method for preparing a photoresist resin, the organic solvent is one or more of methanol, ethanol, dioxane, acetone, methyl ethyl ketone, cyclohexanone, tetrahydrofuran, methyl tetrahydrofuran, benzene, toluene, xylene, chloroform, dichloroethane, and trichloroethane.

Preferably, in the method for preparing the photoresist resin, the precipitant is one or more of pure water, methanol/water mixture, ethanol/water mixture, isopropanol/water mixture, n-heptane, n-hexane, cyclohexane, n-pentane, petroleum ether, diethyl ether, and methyl tert-butyl ether.

Preferably, in the preparation method of the photoresist resin, the temperature-rising reaction condition is 50-90 ℃, the stirring speed is 300-600R/min,

the invention also provides the photoresist resin, which is prepared by the preparation method of the photoresist resin.

The embodiment of the invention provides a photoresist resin and a preparation method thereof, wherein the method comprises the following steps: uniformly mixing at least two acrylate monomers and an organic solvent in a nitrogen environment to obtain a mixed solution, wherein the mass ratio of polar monomers to non-polar monomers in the acrylate monomers is (3-7): (3-7); then adding an initiator into the mixed solution based on a nitrogen environment, stirring, and heating for reaction to obtain a polymer solution; and finally, adding a precipitator into the polymer solution, and performing suction filtration and drying to obtain the photoresist resin. The photoresist resin prepared by the method can well regulate and control the polar component and the non-polar component of the resin, and the photoresist resin has moderate developing solution wettability of a photoresist film and adhesiveness of the photoresist film and a substrate in the application process, and simultaneously reduces excessive loss of the photoresist film in the developing solution.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to specific embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

It should be noted that, in the process of preparing the photoresist resin in the embodiment of the present invention, the weight ratios of the organic solvent, the initiator, and the acrylate monomer used are all 120: 50: 3: 500.

the photoresist resin provided by the invention is prepared by carrying out polymerization reaction on at least one polar acrylate monomer and at least one non-polar acrylate monomer, wherein the mass ratio of the polar acrylate monomer to the non-polar acrylate monomer is controlled to be (3-7): (3-7) so that the polarity and the non-polarity in the generated photoresist resin after the polymerization reaction are balanced, the developing solution wettability of the photoresist film and the adhesion between the photoresist film and the substrate are moderate, and the excessive loss of the photoresist film in the developing solution is reduced. In addition, the polar acrylate monomer and the nonpolar acrylate monomer are subjected to water removal treatment before reaction, so that the error of the actually generated photoresist resin is controlled to be 0-2%, and the requirements of the polarity and the nonpolar balance of the photoresist resin are further met.

Example one

The present embodiment provides a method for preparing a photoresist resin, including the steps of:

pretreatment: uniformly mixing a polar acrylate monomer, a nonpolar acrylate monomer and n-hexane in a nitrogen environment to obtain a mixed solution, wherein the mass ratio of the nonpolar acrylate monomer to the polar acrylate monomer is 7: 12; the specific structure of the nonpolar acrylate monomer is as follows:the specific structure of the polar acrylate monomer is as follows:both the polar acrylate monomer and the non-polar acrylate monomer are subjected to water removal treatment, the water concentration in the monomers is 81ppm and 75ppm respectively, and the purity is 98% and 99% respectively;

synthesis of photoresist resin: adding benzoyl peroxide into the mixed solution under a nitrogen environment, and carrying out stirring reaction for 8 hours at the temperature of 85 ℃ at 450R/min to obtain a polymer solution;

and (3) separation and purification of the photoresist resin: adding methanol into the polymer solution, filtering the solution by using a Buchner funnel, and drying the filtered solid in a vacuum drying oven at 50 ℃ for 48 hours to obtain the photoresist resin, wherein the molecular weight of the photoresist resin is 9000, the PDI distribution is 1.81, and the error range is 2.1% and the product yield is 85%.

After the photoresist resin prepared above was dissolved, a coating film was formed, wherein the coating film rotation speed was 1500rpm, the baking time was 500s, and the temperature was 100 ℃, and a uniform coating film having a thickness of 120nm was obtained, and after the coating film was subjected to contact angle measurement, the contact angle to water was measured to be 83 degrees.

Example two

The present embodiment provides a method for preparing a photoresist resin, including the steps of:

pretreatment: uniformly mixing two polar acrylate monomers, two nonpolar acrylate monomers and tetrahydrofuran in a nitrogen environment to obtain a mixed solution, wherein the mass ratio of the two nonpolar acrylate monomers to the two polar acrylate monomers is 3: 4: 8: 2, the specific structures of the corresponding two nonpolar acrylate monomers are as follows:the concrete structures of the corresponding two polar acrylate monomers are as follows in sequence: the water concentrations of the corresponding two polar acrylate monomers and the two nonpolar acrylate monomers are 65ppm, 72ppm, 57ppm and 79ppm in sequence, and the purities are 98%, 99% and 98% respectively;

synthesis of photoresist resin: adding benzoyl peroxide into the mixed solution under a nitrogen environment, and carrying out stirring reaction for 8 hours at the temperature of 85 ℃ at 450R/min to obtain a polymer solution;

and (3) separation and purification of the photoresist resin: after adding methanol into the polymer solution and filtering the solution by using a Buchner funnel, putting the filtered solid in a vacuum drying oven at 50 ℃ for drying for 48 hours to obtain the photoresist resin, wherein the molecular weight of the photoresist resin is 9000, the PDI distribution is 1.92, and the error range is 2.3 percent, and the product yield is 75 percent.

After the photoresist resin prepared above was dissolved, a coating film was formed, wherein the coating film rotation speed was 1500rpm, the baking time was 500s, and the temperature was 100 ℃, and a uniform coating film having a thickness of 115nm was obtained, and after the coating film was subjected to contact angle measurement, the contact angle to water was measured to be 86 degrees.

In the preparation method of the photoresist resin provided by the embodiment of the invention, at least two acrylate monomers and an organic solvent are uniformly mixed in a nitrogen environment to obtain a mixed solution, wherein the mass ratio of polar monomers to non-polar monomers in the acrylate monomers is (3-7): (3-7); then adding an initiator into the mixed solution based on a nitrogen environment, stirring, and heating for reaction to obtain a polymer solution; and finally, adding a precipitator into the polymer solution, and performing suction filtration and drying to obtain the photoresist resin. The photoresist resin prepared by the method can well regulate and control the polar component and the non-polar component of the photoresist resin, and the photoresist resin enables the developing solution wettability of the photoresist film and the adhesiveness of the photoresist film and the substrate to be moderate in the application process, and simultaneously reduces the excessive loss of the photoresist film in the developing solution.

While the invention has been described with reference to specific embodiments, the invention is not limited thereto, and various equivalent modifications and substitutions can be easily made by those skilled in the art within the technical scope of the invention.