Photoresist resin monomer and synthetic method and application thereof
阅读说明：本技术 一种光刻胶树脂单体及其合成方法和应用 (Photoresist resin monomer and synthetic method and application thereof ) 是由 傅志伟 潘新刚 薛富奎 刘司飞 纪兴跃 李静 于 2021-06-22 设计创作，主要内容包括：本发明属于光刻胶树脂单体,公开了一种光刻胶树脂单体及其合成方法和应用,涉及光刻胶领域,所述树脂单体的结构为式Ⅰ：该结构中,n为1～10的整数,R1为氢、甲基或者氟代烷烃,R2为氢或者一价有机基团,且R2为一价有机基时,R2通过与相邻的O原子形成酯基或者碳酸酯基与多元环相连,且该结构的多元环上的氢原子可以被1～10个碳原子数的烷基取代。本发明提供了一种新的光刻胶树脂单体,有利于改善光刻图形的线宽粗糙度、焦点深度(DOF)和断面的矩形性,并且可以在一定程度上抑制光刻过程后烘导致的模收缩,提高光刻图形的分辨率。(The invention belongs to a photoresist resin monomer, discloses a photoresist resin monomer and a synthetic method and application thereof, and relates to the field of photoresist, wherein the structure of the resin monomer is as shown in formula I:)
1. A photoresist resin monomer is characterized in that the structure of the resin monomer is shown as formula I:
wherein n is an integer of 1-10, R1Is hydrogen, methyl or fluoroalkane, R2Is hydrogen or a monovalent organic radical, and R2In the case of a monovalent organic radical, R2Attached to the polycyclic ring by forming an ester group or a carbonate group with an adjacent O atom; and the hydrogen atoms on the polycyclic ring may be substituted with an alkyl group having 1 to 10 carbon atoms.
2. The photoresist resin monomer of claim 1, wherein the formula i is selected from one of the following formulae ii, iii, and iv:
wherein n is 1 or 2, R3Is alkyl, R1Is hydrogen, methyl or trifluoromethyl.
3. The photoresist resin monomer of claim 2, wherein the resin monomer is selected from the following structures:
wherein R is1Is hydrogen, methyl or trifluoromethyl.
4. The photoresist resin monomer according to claim 3, wherein the resin monomer is specifically selected from the following structures:
5. a synthetic method of a photoresist resin monomer is characterized in that the photoresist resin monomer is a resin monomer of a formula II, and the synthetic method comprises the following steps:
wherein n is 1 or 2, R1Is hydrogen, methyl or trifluoromethyl;
under the protection of inert gas, adding titanium dichloride and 1 zinc into dichloromethane, adding trimethyl acetonitrile, cooling to 0-5 ℃, adding a dichloromethane solution of cyclic ketone II-1, reacting at 20-30 ℃, and performing post-treatment and purification to obtain an intermediate II-2;
and b, under an alkaline condition, carrying out esterification reaction on the intermediate II-2 and acryloyl chloride or substituted acryloyl chloride in dichloromethane, and carrying out post-treatment and purification to obtain the resin monomer shown in the formula II.
6. The method for synthesizing the photoresist resin monomer according to claim 5, wherein the photoresist resin monomer is a resin monomer of formula III, and the synthesis method comprises:
wherein n is 1 or 2, R3Is alkyl, R1Is hydrogen, methyl or trifluoromethyl;
and c, under the alkaline condition, carrying out esterification reaction on 1 equivalent of the resin monomer shown in the formula II and alkyl acyl chloride in dichloromethane, and carrying out post-treatment and purification to obtain the resin monomer shown in the formula III.
7. The method for synthesizing the photoresist resin monomer according to claim 5, wherein the photoresist resin monomer is a resin monomer of formula IV, and the synthesizing method comprises:
wherein n is 1 or 2, R3 is alkyl, R1 is hydrogen, methyl or trifluoromethyl;
and d, reacting the resin monomer shown in the formula II with an anhydride compound in a solvent II under an alkaline condition, and carrying out post-treatment and purification to obtain the resin monomer shown in the formula IV.
8. The method for synthesizing a photoresist resin monomer of claim 5, wherein the substituted acryloyl chloride in step b is methacryloyl chloride or trifluoromethylacryloyl chloride.
9. A photoresist resin monomer according to any one of claims 1 to 4 for use in the preparation of photoresists.
Technical Field
The invention relates to the field of photoresist, and discloses a photoresist resin monomer, and a preparation method and application thereof.
Background
The photolithography technique is a fine processing technique for transferring a pattern designed on a mask plate to a pattern on a substrate by using the chemical sensitivity of a photolithography material (particularly a photoresist) under the action of visible light, ultraviolet rays, electron beams and the like through the processes of exposure, development, etching and the like.
The main components of the photoresist material are resin, photoacid generator, and corresponding additives and solvents, and the material has chemical sensitivity with light (including visible light, ultraviolet light, electron beam, etc.) and changes its solubility in developer through photochemical reaction. According to the difference of photochemical reaction mechanism, the photoresist is divided into a positive photoresist and a negative photoresist: after exposure, the solubility of the photoresist in a developing solution is increased, and the photoresist with the same pattern as that of the mask is obtained and is called as positive photoresist; after exposure, the photoresist has reduced solubility or even no solubility in a developing solution, and a negative photoresist with a pattern opposite to that of the mask is obtained.
With the development of the photolithography technology, the size requirement of the photolithography pattern is smaller and smaller, and the resolution and the edge roughness of the photolithography pattern are also more required, and it is necessary to develop a new photolithography resist.
Disclosure of Invention
It is another object of the present invention to provide a photoresist resin monomer, and to provide a method for preparing the same.
In order to achieve the purpose, the invention adopts the following technical scheme:
a photoresist resin monomer, the structure of the resin monomer is as formula I:
in the structure, n is an integer of 1-10, R1Is hydrogen, methyl or fluoroalkane, R2Is hydrogen or a monovalent organic radical, and R2In the case of a monovalent organic radical, R2The hydroxyl group is connected with the polycyclic ring through forming an ester group or a carbonate group with an adjacent O atom, and the hydrogen atom on the polycyclic ring of the structure can be substituted by alkyl with 1-10 carbon atoms.
More preferably formula I is selected from one of the following formulae II, III and IV:
wherein n is 1 or 2, R3Is alkyl, R1Is hydrogen, methyl or trifluoromethyl.
Further, the resin monomer is specifically selected from the following structures but is not limited to the following structures:
in the above structure, R1Is hydrogen, methyl or trifluoromethyl.
The resin monomer is specifically selected from the following structures:
in addition, a method for synthesizing the resin monomer of the formula II is provided:
wherein n is 1 or 2, R1Is hydrogen, methyl or trifluoromethyl;
under the protection of inert gas, adding titanium dichloride and zinc into dichloromethane, then adding trimethyl acetonitrile, cooling to 0-5 ℃, then adding a dichloromethane solution of cyclic ketone II-1, reacting at 20-30 ℃, and performing post-treatment and purification to obtain an intermediate II-2;
b, under the alkaline condition, carrying out esterification reaction on the intermediate II-2 and acryloyl chloride or substituted acryloyl chloride in dichloromethane, and carrying out post-treatment and purification to obtain a resin monomer shown in the formula II;
further, the synthesis method of the resin monomer shown in the formula III comprises the following steps:
wherein n is 1 or 2, R3Is alkyl, R1Is hydrogen, methyl or trifluoromethyl;
and c, under the alkaline condition, carrying out esterification reaction on the resin monomer shown in the formula II and alkyl acyl chloride in dichloromethane, and carrying out post-treatment and purification to obtain the resin monomer shown in the formula III.
Further, the synthesis method of the resin monomer shown in the formula IV comprises the following steps:
wherein n is 1 or 2, R3 is alkyl, R1 is hydrogen, methyl or trifluoromethyl;
and d, reacting the resin monomer shown in the formula II with an anhydride compound in a solvent II under an alkaline condition, and carrying out post-treatment and purification to obtain a resin monomer IV.
Further, the substituted acryloyl chloride in the step b is methacryloyl chloride or trifluoromethyl acryloyl chloride.
The photoresist resin monomer is used for preparing photoresist.
Compared with the prior art, the invention has the following beneficial effects: the resin monomer can be polymerized with other resin monomers to form photoresist resin, which is beneficial to improving the line width roughness, the depth of focus (DOF) and the rectangularity of a cross section of a photoetching pattern, and can inhibit the mold shrinkage caused by baking after a photoetching process to a certain extent and improve the resolution of the photoetching pattern.
Detailed Description
The technical solutions in the embodiments of the present invention will be described below clearly and completely in connection with the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments.
Example 1
Under nitrogen protection, titanium dichloride (7.1g, 59.8mmol) and zinc (4g, 61.2mmol) are added to dichloromethane (50mL), trimethylacetonitrile (19.8g, 238mmol) is added, the mixture is cooled to 0 ℃, a solution of cyclopentanone (5g, 59.4mmol) in dichloromethane (5mL) is added to the reaction solution, the reaction is continued at 25 ℃ for 16 hours under nitrogen protection, saturated ammonium chloride (20mL) is added to the reaction solution, the reaction solution is quenched, extracted with dichloromethane (20 mL. times.3), the organic phases are combined, washed successively with saturated sodium bicarbonate (20mL), saturated brine (20mL), dried over anhydrous sodium sulfate and concentrated under vacuum to give a crude product, which is purified by column chromatography to give intermediates 1-2(8.4g, 49.3mmol, 83.0%).
Adding the intermediate 1-2(2g, 11.7mmol) into dichloromethane (15mL), adding triethylamine (3.6g, 35.6mmol), cooling to 0 ℃, slowly dropwise adding acryloyl chloride (1.1g, 12.2mmol), heating to 25 ℃, continuing stirring for 2 hours, cooling the reaction liquid to 0-5 ℃ with ice water, adding an aqueous solution of sodium bicarbonate (10mL), extracting with dichloromethane (10mL × 3), combining organic phases, washing the organic phase with saturated sodium chloride (15mL), drying with anhydrous sodium sulfate, concentrating in vacuum, and purifying by column chromatography to obtain a resin monomer M1(2.5g, 11.1mmol, 94.9%).
Example 2
Resin monomer M1(2g, 8.9mmol) was dissolved in dichloromethane (15mL), triethylamine (1.5g, 13.6mmol) was added, cooling to 0 deg.C, a solution of acetyl chloride (0.7g, 8.9mmol) in dichloromethane (3mL) was added dropwise, stirring was carried out at 25 deg.C for 2 hours, a saturated solution of sodium bicarbonate (10mL) was added, extraction was carried out with dichloromethane (10 mL. times.3), the organic phases were combined and washed with saturated sodium chloride, dried over anhydrous sodium sulfate, and concentrated in vacuo to give a crude product which was purified by column chromatography to give resin monomer M2(2.2g, 8.3mmol, 92.6%).
Example 3
Dissolving resin monomer M1(2g, 8.9mmol) in dichloromethane (15mL), adding 4-dimethylaminopyridine (20mg, 0.2mmol) and triethylamine (1.5g, 13.6mmol), cooling to 0 deg.C, slowly adding oxalyl chloride monoethyl ester (1.3g, 9.5mmol), after the dropwise addition, raising to 25 deg.C, stirring for 2 hours, adding saturated sodium bicarbonate solution (10mL), extracting with dichloromethane (15 mL. times.3), combining the organic phases, washing with saturated sodium chloride, drying with anhydrous sodium sulfate, vacuum concentrating to obtain crude product, and purifying by column chromatography to obtain resin monomer M3(2.6g, 8.0mmol, 89.9%).
Example 4
Dissolving a resin monomer M1(2g, 8.9mmol) in acetonitrile (15mL), adding 4-dimethylaminopyridine (20mg, 0.2mmol), cooling to 0 ℃, slowly dropwise adding di-tert-butyl dicarbonate (2.3g, 10.5mmol), raising the temperature to 25 ℃, stirring for three hours, cooling the reaction liquid to 0-5 ℃, adding a saturated aqueous solution of sodium bicarbonate, extracting with ethyl acetate (10mL multiplied by 3), mixing the organic phases, and washing with saturated sodium chloride (20 mL); after drying over anhydrous sodium sulfate, concentration in vacuo afforded the crude product, which was purified by column chromatography to afford resin monomer M4(2.6g, 8.0mmol, 89.9%).
Example 5
The synthesis was carried out in the same manner as in example 1 to obtain resin monomer M5(9.5g, 37.7mmol, 92.2%).
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and equivalent alternatives or modifications according to the technical solution and the inventive concept of the present invention should be covered by the scope of the present invention.