阅读说明：本技术 一种由2-环戊基环戊酮合成的可降解型树脂单体及其制备方法和应用 (Degradable resin monomer synthesized from 2-cyclopentyl cyclopentanone and preparation method and application thereof ) 是由 傅志伟 邵严亮 余文卿 薛富奎 刘司飞 李静 于 2021-06-24 设计创作，主要内容包括：本发明涉及光刻胶技术领域,公开了一种由2-环戊基环戊酮合成的可降解型树脂单体及其制备方法和应用,所述可降解型树脂单体的结构通式如下：其中R为烷基或杂烷基。可降解型树脂单体上含有叔丁基结构,在曝光时,光致产酸剂会产生酸,在酸的作用下,叔丁基结构会断开,导致聚合主链断开,形成小片段,能够改善光刻图形的边缘粗糙度,提高光刻胶的分辨率,断开后形成了具有良好碱溶性的羟基,有利于显影过程中的溶解,增加曝光后光刻胶在显影液中溶解速度,增大光刻胶的对比度。(The invention relates to the technical field of photoresist, and discloses a degradable resin monomer synthesized by 2-cyclopentyl cyclopentanone, a preparation method and application thereof, wherein the structural general formula of the degradable resin monomer is as follows:)

1. A degradable resin monomer synthesized by 2-cyclopentyl cyclopentanone is characterized in that the structural general formula of the degradable resin monomer is as follows:

wherein R is alkyl or heteroalkyl.

2. The degradable resin monomer synthesized from 2-cyclopentyl cyclopentanone of claim 1, wherein the degradable resin monomer is selected from the following structures:

or

3. A preparation method of a degradable resin monomer synthesized from 2-cyclopentyl cyclopentanone is characterized in that the synthetic route of the degradable resin monomer is as follows:

wherein R is alkyl or heteroalkyl, and R' is a protecting group.

The method comprises the following synthetic steps:

s1, protecting hydroxyl of the raw material I by a protecting group to obtain an intermediate II;

s2, 2-cyclopentyl cyclopentanone is reduced under the condition of a Grignard reagent formed by the intermediate II and metal to obtain an intermediate III containing a hydroxyl;

s3, deprotecting the intermediate III to obtain an intermediate IV containing two hydroxyl groups;

and S4, carrying out esterification reaction on the intermediate IV and an acrylic acid compound to obtain a degradable resin monomer V.

4. The method for preparing the degradable resin monomer synthesized from 2-cyclopentyl cyclopentanone according to claim 3, wherein: in S1, hydroxyl of the raw material I is protected by benzyl or silyl ether to obtain an intermediate II.

5. The method for preparing the degradable resin monomer synthesized from 2-cyclopentyl cyclopentanone according to claim 3, wherein: the raw material I is specifically selected from the following structures:

or

6. The use of the degradable resin monomer synthesized from 2-cyclopentyl cyclopentanone according to any of claims 1-2 in the preparation of a photoresist.

Technical Field

The invention relates to the technical field of photoresist, in particular to a degradable resin monomer synthesized by 2-cyclopentyl cyclopentanone, 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 a 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.

The existing resin monomer has low etching resistance, and the solubility of the photoresist in a developing solution is insufficient after exposure, so that a degradable resin monomer synthesized by 2-cyclopentyl cyclopentanone and a preparation method thereof are provided.

Disclosure of Invention

Aiming at the defects in the prior art, the invention provides a degradable resin monomer synthesized by 2-cyclopentyl cyclopentanone, and a preparation method and application thereof.

The invention provides the following technical scheme: a degradable resin monomer synthesized by 2-cyclopentyl cyclopentanone, wherein the degradable resin monomer has the following structural general formula:

wherein R is alkyl or heteroalkyl.

Preferably, the degradable resin monomer is selected from the following structures:

or

The preparation method of the degradable resin monomer synthesized from 2-cyclopentyl cyclopentanone comprises the following specific synthetic route:

wherein R is alkyl or heteroalkyl, and R' is a protecting group.

The method comprises the following synthetic steps:

s1, protecting hydroxyl of the raw material I by a protecting group to obtain an intermediate II;

s2, 2-cyclopentyl cyclopentanone is reduced under the condition of a Grignard reagent formed by the intermediate II and metal to obtain an intermediate III containing a hydroxyl;

s3, deprotecting the intermediate III to obtain an intermediate IV containing two hydroxyl groups;

and S4, carrying out esterification reaction on the intermediate IV and an acrylic acid compound to obtain a degradable resin monomer V.

Preferably, in S1, the hydroxyl group of the raw material I is protected by benzyl or silyl ether to obtain an intermediate II.

Preferably, the starting material i is selected in particular from the following structures:or

The degradable resin monomer synthesized from 2-cyclopentyl cyclopentanone is used for preparing the photoresist.

Compared with the prior art, the degradable resin monomer synthesized by 2-cyclopentyl cyclopentanone and the preparation method thereof have the following beneficial effects:

(1) the degradable resin monomer contains a tert-butyl structure, the photoacid generator can generate acid during exposure, the tert-butyl structure can be broken under the action of the acid, so that a polymerization main chain is broken, small segments are formed, the edge roughness of a photoetching pattern can be improved, the resolution of the photoresist is improved, and meanwhile, hydroxyl with good alkali solubility is formed after the tert-butyl structure is broken, so that the dissolution in the developing process is facilitated, the dissolution speed of the photoresist in a developing solution after exposure is increased, and the contrast of the photoresist is increased;

(2) the annular structure of the 2-cyclopentyl cyclopentanone also greatly increases the etching resistance of the photoresist, and the polyester-based structure of the resin monomer also increases the solubility of the resin monomer in a fat-soluble solvent, so that the spin coating is convenient and uniform;

(3) the invention has simple synthetic route and convenient operation.

Detailed Description

To make the objects, technical solutions and advantages of the embodiments of the present disclosure clearer and to describe more fully technical solutions of the embodiments of the present disclosure, and to keep the following description of the embodiments of the present disclosure clear and concise, detailed descriptions of known functions and known parts of the disclosure are omitted so as to avoid unnecessarily obscuring the concepts of the present disclosure.

A degradable resin monomer synthesized by 2-cyclopentyl cyclopentanone, wherein the degradable resin monomer has the following structural general formula:

wherein R is alkyl or heteroalkyl.

The degradable resin monomer has the following structure:

or

A preparation method of a degradable resin monomer synthesized from 2-cyclopentyl cyclopentanone comprises the following specific synthetic route:

wherein R is alkyl or heteroalkyl, and R' is a protecting group.

The method comprises the following synthetic steps:

s1, protecting hydroxyl of the raw material I by a protecting group to obtain an intermediate II;

s2, 2-cyclopentyl cyclopentanone is reduced under the condition of a Grignard reagent formed by the intermediate II and metal to obtain an intermediate III containing a hydroxyl;

s3, deprotecting the intermediate III to obtain an intermediate IV containing two hydroxyl groups;

and S4, carrying out esterification reaction on the intermediate IV and an acrylic compound to obtain a resin monomer V.

In S1, hydroxyl of the raw material I is protected by benzyl or silyl ether to obtain an intermediate II.

The starting material I specifically comprises a structure selected from:or

Example 1

Preparation of Compounds 1-2:

tert-butyldimethylsilyl chloride (13g, 86.3mmol) was dissolved in tetrahydrofuran (50g), and the above mixture was added dropwise to tetrahydrofuran (100g) containing 2-bromoethanol 1-1(10g, 80.0mmol) under nitrogen protection at 0 ℃ and stirred for 3 hours. The resulting suspension was filtered to obtain a filtrate, the filtrate was concentrated, and compound 1-2(15g, 62.7mmol, molar yield 78.4%) was purified by distillation under reduced pressure.

Preparation of Compounds 1-3:

compound 1-2(15g, 62.7mmol) was dissolved in diethyl ether (100g), and the above mixture was added dropwise to diethyl ether (30g) containing magnesium (1.5g,62.5mmol) under nitrogen, and stirred at 25 ℃ for 1 hour. 2-Cyclopentylcyclopentanone (9g, 59.1mmol) was dissolved in diethyl ether (80g), added dropwise to the above mixture, and stirred for 3 hours. The reaction was quenched, then filtered, the filtrate was extracted with ethyl acetate, the resulting organic layers were combined, washed with brine, dried over anhydrous sodium sulfate, and concentrated to give a crude product. The crude product was recrystallized from ethyl acetate and hexane to give compound 1-3(15.5g, 49.6mmol, 83.9% molar yield).

Preparation of Compounds 1-4:

a1 Mol/L tetrahydrofuran solution of tetrabutylammonium fluoride (54mL, 54mmol) was added dropwise to tetrahydrofuran (100g) containing compound 1-3(15.5g, 49.6mmol) at 25 ℃ under nitrogen, and stirred for 3 hours. The reaction was quenched with saturated ammonium chloride solution, extracted with ethyl acetate, and the combined organic phases were concentrated to give a crude product which was purified by silica gel column to give compounds 1-4(8.5g, 42.9mmol, 86.4% molar yield).

Preparation of degradable resin monomers 1-5:

compounds 1-4(8.5g, 42.9mmol), triethylamine (9g, 88.9mmol) were dissolved in dichloromethane (150g), methacryloyl chloride (9g, 86.1mmol) was added dropwise to the mixture, stirred at 0 ℃ under nitrogen for 30 minutes, and then stirred at room temperature for 4 hours. Filtering, concentrating the filtrate to obtain crude product, and purifying the crude product by column chromatography to obtain degradable resin monomer 1-5(12g, 35.9mmol, molar yield 83.7%).

Example 2

Preparation of Compound 2-2:

tert-butyldimethylchlorosilane (10g, 66.3mmol) was dissolved in tetrahydrofuran (50g), and the above mixture was dropwise added to tetrahydrofuran (100g) containing 3-bromomethyl-3-hydroxymethyl-1-oxetane 2-1(10g, 55.2mmol) under nitrogen protection at 0 ℃ and stirred for 3 hours. The resulting suspension was filtered to obtain a filtrate, the filtrate was concentrated, and compound 2-2(13.5g, 45.7mmol, molar yield 82.8%) was purified by distillation under reduced pressure.

Preparation of Compounds 2-3:

compound 2-2(13.5g, 45.7mmol) was dissolved in diethyl ether (100g), and the above mixture was added dropwise to diethyl ether (30g) containing magnesium (1.2g,50mmol) under nitrogen atmosphere, and stirred at 25 ℃ for 1 hour. 2-Cyclopentylcyclopentanone (7g, 46.0mmol) was dissolved in diethyl ether (80g), and the solution was added dropwise to the mixture and stirred for 3 hours. The reaction was quenched, then filtered, the filtrate was extracted with ethyl acetate, the resulting organic layers were combined, washed with brine, dried over anhydrous sodium sulfate, and concentrated to give a crude product. The crude product was recrystallized from ethyl acetate and hexane to give compound 2-3(13.5g, 36.6mmol, 79.6% molar yield).

Preparation of Compounds 2-4:

a1 Mol/L tetrahydrofuran solution (38mL, 38mmol) of tetrabutylammonium fluoride was added dropwise to 100g of tetrahydrofuran containing 2-3(13.5g, 36.6mmol) under nitrogen protection at 25 ℃ and stirred for 3 hours. The reaction solution was quenched with saturated ammonium chloride solution, extracted with ethyl acetate, the combined organic phases were concentrated to give a crude product, which was purified by silica gel column to give compound 2-4(8g, 31.5mmol, 85.9% molar yield).

Preparation of degradable resin monomer 2-5:

compound 2-4(8g, 31.5mmol), triethylamine (7g, 69.2mmol) were dissolved in dichloromethane (150g), methacryloyl chloride (7g, 67.0mmol) was added dropwise to the above mixture, stirred at 0 ℃ under nitrogen for 30 minutes, and then stirred at room temperature for 4 hours. Filtering, concentrating the filtrate to obtain crude product, and purifying the crude product by column chromatography to obtain degradable resin monomer 2-5(9.5g, 24.3mmol, molar yield 77.4%).

The above embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and the scope of the present invention is defined by the claims. Various modifications and equivalents may be made by those skilled in the art within the spirit and scope of the present invention, and such modifications and equivalents should also be considered as falling within the scope of the present invention.