CN112552298A - Sulfonium salt photo-acid generator synthesized from 16-epi-NB-methyl Voacarpine base and preparation method thereof - Google Patents
Sulfonium salt photo-acid generator synthesized from 16-epi-NB-methyl Voacarpine base and preparation method thereof Download PDFInfo
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- CN112552298A CN112552298A CN202011548485.XA CN202011548485A CN112552298A CN 112552298 A CN112552298 A CN 112552298A CN 202011548485 A CN202011548485 A CN 202011548485A CN 112552298 A CN112552298 A CN 112552298A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
- C07D471/08—Bridged systems
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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Abstract
The invention belongs to the technical field of photoresist, and discloses a sulfonium salt photo-acid generator synthesized by 16-epi-NB-methyl Voacarpine and a preparation method thereof. The sulfonium salt photo-acid generator synthesized by 16-epi-NB-methyl Voacarpine base comprises the following general structure:
R1is a linking group, R2Is a hydrocarbon group or a fluorine-containing hydrocarbon group, P1、P2And P3Independently of one another, represents hydrogen or optionally substituted alkyl having 1 to 12 carbon atoms. The synthesis steps are as follows: reacting 16-epi-NB-methyl Voacarpine with sulfoacetate compound or with bis (trichloromethyl) carbonate and hydroxyethanesulfonic acid compound to form a medium containing 16-epi-NB-methyl Voacarpine base structure and sulfonic acid structureAn intermediate; and (3) carrying out ion exchange reaction on the intermediate and sulfonium halide, and purifying reaction liquid to obtain the photoacid generator containing a 16-epi-NB-methyl Voacarbone alkali structure. The sulfonium salt photo-acid generator synthesized by the invention has low diffusion and hydrophilic-lipophilic balance, and the preparation method is simple.
Description
Technical Field
The invention relates to the technical field of photoresist, in particular to a photoacid generator synthesized by 16-epi-NB-methyl Voacarpine base.
Background
The photolithography material (specifically referred to as photoresist), also called photoresist, is the most critical functional chemical material involved in photolithography technology, and the main components are resin, Photo Acid Generator (PAG), and corresponding additives and solvents.
As the feature size of Integrated Circuits (ICs) is gradually reduced, the influence of the acid diffusion length on the lithography pattern becomes more and more significant, including low mask fidelity, deterioration of LWR (Line Width Roughness), and deterioration of pattern rectangularity. The structure of the PAG anion has been found to play an important role in the overall performance of the photoresist by affecting the interaction between the PAG and other photoresist components. These interactions affect the diffusion characteristics of the photogenerated acid. It is therefore very important to prepare photoacid generators (PAGs) with controllable acid diffusivity.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a sulfonium salt photo-acid generator synthesized by 16-epi-NB-methyl Voacarpine and a preparation method thereof.
In order to solve the technical problems, the invention provides the following technical scheme:
the invention provides a photoacid generator synthesized from 16-epi-NB-methyl Voacarpine base, which comprises the following general structure:
wherein R is1Is a linking group, R2Is a hydrocarbon group or a fluorine-containing hydrocarbon group; p1、P2And P3Independently of one another, represents hydrogen or optionally substituted alkyl having 1 to 12 carbon atoms.
As a preferable technical means of the present invention, R is1Is an ester group or a carbonate group.
As a preferred embodiment of the present invention, the anion comprises the following structure:
As a preferred embodiment of the present invention,
the preparation method of the sulfonium salt photo-acid generator synthesized by 16-epi-NB-methyl Voacarpine base comprises the following steps:
s1, carrying out esterification reaction on the 16-epi-NB-methyl Voacarbone alkali I and a sulfoacetate compound under the condition of a catalyst, and purifying to obtain an intermediate II containing a 16-epi-NB-methyl Voacarbone alkali structure and a sulfonate structure;
s2, carrying out ion exchange reaction on the intermediate II and halogenated sulfonium, and purifying reaction liquid to obtain a sulfonium salt photo-acid generator III containing a 16-epi-NB-methyl Voacarbone alkali structure;
the method comprises the following synthetic routes:
wherein R is1Is an ester group, R2Is a hydrocarbon group or a fluorine-containing hydrocarbon group; p1、P2And P3Independently of one another, represents hydrogen or optionally substituted alkyl having 1 to 12 carbon atoms; m is an alkali metal.
In a preferred embodiment of the present invention, the sulfoacetate compound in S1 is sodium carboxydifluoromethanesulfonate and sodium carboxymethylsulfonate.
As a preferred embodiment of the present invention, S1 is replaced with: reacting 16-epi-NB-methyl Voacarbone alkali I with bis (trichloromethyl) carbonate and a hydroxyethanesulfonic compound under an alkaline condition, and purifying to obtain an intermediate II containing a 16-epi-NB-methyl Voacarbone alkali structure and a sulfonic acid structure; the synthetic route is as follows:
wherein R is1Is a carbonate group, R2Is a hydrocarbon group or a fluorine-containing hydrocarbon group; m is an alkali metal.
As a preferable technical scheme of the invention, the hydroxyethanesulfonic acid compound is 1, 1-difluoro-2-hydroxy-ethanesulfonic acid sodium salt.
Preferably, the sulfonium halides in S2 are triphenylsulfonium bromide, tri-p-tolylsulfonium chloride and triphenylsulfonium chloride.
Compared with the prior art, the invention has the following beneficial effects:
(1) the sulfonium salt type photoacid generator synthesized by the 16-epi-NB-methyl Voacarpine base, provided by the invention, has the advantages that the anion comprises a 16-epi-NB-methyl Voacarpine base structure and an ester group structure, the molecular weight of the 16-epi-NB-methyl Voacarpine base is 382.45, the molecular weight is larger, the diffusion of the photoacid generator can be reduced, the edge roughness of a photoresist can be reduced, and the 16-epi-NB-methyl Voacarpine base is an alkaloid and can inhibit the diffusion of the photoacid generator. The ester group structure can increase the lipid solubility of the photoacid generator in resin and solvent, form photoresist which is dissolved uniformly, is beneficial to imaging, also enables the photoacid generator to have certain hydrophilicity, and can be well adhered to a silicon wafer.
(2) The invention takes 16-epi-NB-methyl Voacarbone as a raw material, and the 16-epi-NB-methyl Voacarbone is a green natural product, has no pollution, and is simple and easy to obtain.
(3) The synthesis process is simple and convenient to operate.
Detailed Description
It should be understood that the preferred embodiments described herein are for purposes of illustration and explanation only and are not intended to limit the present invention.
Example 1
The photoacid generator 1-3 prepared by taking 16-epi-NB-methyl Voacarpine as a raw material has the following synthetic route:
the method comprises the following specific steps:
s1, sodium carboxydifluoromethanesulfonate (26.3mmol, 5.2g), dicyclohexylcarbodiimide (26.2mmol,5.4g) and 4-dimethylaminopyridine (4.09mmol,0.5g) were added to a solution of 16-epi-NB-methylvoacarpine base 1-1(26.1mmol,10g) in dichloromethane (150g), followed by stirring at room temperature for 24 hours. The reaction solution was concentrated, and the residue was slurried in methyl t-butyl ether, the above mixture was filtered, and the dried cake was collected to give compound 1-2 as a solid (19.6mmol, 11g, yield 74.8%).
S2, Compound 1-2(19.6mmol, 11g) and triphenylsulfonium bromide (19.5mmol,6.7g) were dissolved in a mixed solvent of dichloromethane (80g) and water (80 g). The mixture was stirred at 30 ℃ for 24 hours. The reaction solution was washed with deionized water and the organic solvent was evaporated off, after which the residue obtained was dissolved in dichloromethane and added to methyl tert-butyl ether for pulping. The resulting solid was vacuum filtered, washed with methyl tert-butyl ether and vacuum dried to give 1-3(16.2mmol, 13g, 82.8% yield) of an off-white solid photoacid generator.
Example 2
2-3 of a photoacid generator prepared by taking 16-epi-NB-methyl Voacarpine as a raw material, wherein the synthetic route is as follows:
the method comprises the following specific steps:
s1, sodium carboxymethyl sulfonate (26.5mmol,4.3g), dicyclohexylcarbodiimide (26.2mmol,5.4g) and 4-dimethylaminopyridine (4.09mmol,0.5g) were added to a solution of 16-epi-NB-methylvoacarpine base 2-1(26.1mmol,10g) in dichloromethane (150g), followed by stirring at room temperature for 24 hours. The reaction solution was concentrated, and the residue was added to methyl t-butyl ether for beating, and the above-mentioned mixture was filtered, and the dried cake was collected to obtain compound 2-2(18.0mmol, 9.5g, 69.0%) as a solid.
S2, Compound 2-2(18.0mmol, 9.5g) and tri-p-tolylsulfonium chloride (18.2mmol,6.2g) were dissolved in a mixed solvent of dichloromethane (80g) and water (80 g). The mixture was stirred at 30 ℃ for 24 hours. The reaction solution was washed with deionized water and the organic solvent was evaporated off, after which the residue obtained was dissolved in dichloromethane and added to methyl tert-butyl ether for pulping. The resulting solid was vacuum filtered, washed with methyl tert-butyl ether and vacuum dried to give 2-3(14.8mmol, 12g, 82.2% yield) as an off-white solid.
Example 3
3-3 parts of a photoacid generator prepared by taking 16-epi-NB-methyl Voacarpine as a raw material, wherein the synthetic route is as follows:
the method comprises the following specific steps:
s1, pyridine (65.7mmol,5.2g) and bis (trichloromethyl) carbonate (8.76mmol,2.6g) were added to dichloromethane (150g) with stirring at 0 ℃ under nitrogen protection, followed by the slow addition of 16-epi-NB-methyl Voacarbone base 3-1(26.1mmol,10 g). The reaction mixture was stirred at 25 ℃ for 3 hours. Then 1, 1-difluoro-2-hydroxy-ethanesulfonic acid sodium salt (26.1mmol, 4.8g) was added to the reaction solution, and stirred for 10 hours. Concentration by rotary evaporation gave a mixture which was filtered and washed three times with acetonitrile. The mixed acetonitrile solution was concentrated and added to methyl t-butyl ether for beating, and the above-mentioned mixture was filtered, and the dried cake was collected to obtain solid compound 3-2(18.6mmol, 11g, yield 71.0%).
S2, Compound 3-2(18.6mmol, 11g) and triphenylsulfonium chloride (18.7mmol,5.6g) were dissolved in a mixed solvent of dichloromethane (70g) and water (70 g). The mixture was stirred at 30 ℃ for 4 hours. The reaction solution was washed with deionized water and the organic solvent was evaporated off, after which the residue obtained was dissolved in dichloromethane and added to methyl tert-butyl ether for pulping. The resulting solid was vacuum filtered, washed with methyl tert-butyl ether and vacuum dried to give 3-3(15.6mmol, 13g, 84.1% yield) as an off-white solid.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. A sulfonium salt photoacid generator synthesized from 16-epi-NB-methyl voacarpine base, wherein the photoacid generator comprises the following general structure:
wherein R is1Is a linking group, R2Is a hydrocarbon group or a fluorine-containing hydrocarbon group; p1、P2And P3Independently of one another, represents hydrogen or optionally substituted alkyl having 1 to 12 carbon atoms.
2. The photoacid generator of the sulfonium salt family synthesized from 16-epi-NB-methylVoacarpine base as claimed in claim 1, wherein R is1Is an ester group or a carbonate group.
3. The sulfonium salt-based photoacid generator synthesized from 16-epi-NB-methyl voacarpine base of claim 1 or 2, wherein the photoacid generator comprises the following structure:
4. The sulfonium salt-based photoacid generator synthesized from 16-epi-NB-methyl voacarpine base of claim 3, specifically comprising the following structure:
5. a preparation method of a sulfonium salt photo-acid generator synthesized by 16-epi-NB-methyl Voacarpine base is characterized by comprising the following steps:
s1, carrying out esterification reaction on the 16-epi-NB-methyl Voacarbone alkali I and a sulfoacetate compound under the condition of a catalyst, and purifying to obtain an intermediate II containing a 16-epi-NB-methyl Voacarbone alkali structure and a sulfonate structure;
s2, carrying out ion exchange reaction on the intermediate II and halogenated sulfonium, and purifying reaction liquid to obtain a sulfonium salt photo-acid generator III containing a 16-epi-NB-methyl Voacarbone alkali structure; the synthetic route is as follows:
wherein R is1Is an ester group, R2Is a hydrocarbon group or a fluorine-containing hydrocarbon group; p1、P2And P3Independently of one another, represents hydrogen or optionally substituted alkyl having 1 to 12 carbon atoms; m is an alkali metal.
6. The method for producing a sulfonium salt-based photoacid generator synthesized from 16-epi-NB-methyl voacarpine as claimed in claim 5, wherein the sulfoacetate compound in S1 is sodium carboxydifluoromethanesulfonate and sodium carboxymethylsulfate.
7. The method for preparing a sulfonium salt-based photoacid generator synthesized from 16-epi-NB-methylvoacarpine base as claimed in claim 5, wherein S1 is replaced with: reacting 16-epi-NB-methyl Voacarbone alkali I with bis (trichloromethyl) carbonate and a hydroxyethanesulfonic compound under an alkaline condition, and purifying to obtain an intermediate II containing a 16-epi-NB-methyl Voacarbone alkali structure and a sulfonic acid structure;
the synthetic route is as follows:
wherein R is1Is a carbonate group, R2Is a hydrocarbon group or a fluorine-containing hydrocarbon group; m is an alkali metal.
8. The method for preparing a sulfonium salt-based photoacid generator synthesized from 16-epi-NB-methylvoacarpine base as claimed in claim 7, wherein the hydroxyethylsulfonic compound is 1, 1-difluoro-2-hydroxy-ethanesulfonic acid sodium salt.
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| CN112661805A (en) * | 2020-12-23 | 2021-04-16 | 上海博栋化学科技有限公司 | Sulfonium salt photo-acid generator synthesized from Bromus buxus alkali B and preparation method thereof |
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