CN111138406A - Sulfonium sulfonate photo-acid generator synthesized from guaiol and synthesis method thereof - Google Patents
Sulfonium sulfonate photo-acid generator synthesized from guaiol and synthesis method thereof Download PDFInfo
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- CN111138406A CN111138406A CN201911384567.2A CN201911384567A CN111138406A CN 111138406 A CN111138406 A CN 111138406A CN 201911384567 A CN201911384567 A CN 201911384567A CN 111138406 A CN111138406 A CN 111138406A
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- sulfonate
- guaiol
- photoacid generator
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- sulfonium
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- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 title claims abstract description 46
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 title claims abstract description 30
- TWVJWDMOZJXUID-SDDRHHMPSA-N Guaiol Chemical compound C1([C@H](CC[C@H](C2)C(C)(C)O)C)=C2[C@@H](C)CC1 TWVJWDMOZJXUID-SDDRHHMPSA-N 0.000 title claims abstract description 28
- TWVJWDMOZJXUID-QJPTWQEYSA-N guaiol Natural products OC(C)(C)[C@H]1CC=2[C@H](C)CCC=2[C@@H](C)CC1 TWVJWDMOZJXUID-QJPTWQEYSA-N 0.000 title claims abstract description 28
- 239000002253 acid Substances 0.000 title claims abstract description 15
- 238000001308 synthesis method Methods 0.000 title abstract description 7
- -1 sulfonate compound Chemical class 0.000 claims abstract description 30
- 125000004185 ester group Chemical group 0.000 claims abstract description 18
- QAEDZJGFFMLHHQ-UHFFFAOYSA-N trifluoroacetic anhydride Chemical compound FC(F)(F)C(=O)OC(=O)C(F)(F)F QAEDZJGFFMLHHQ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 9
- ISXOBTBCNRIIQO-UHFFFAOYSA-N tetrahydrothiophene 1-oxide Chemical compound O=S1CCCC1 ISXOBTBCNRIIQO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229940094989 trimethylsilane Drugs 0.000 claims abstract description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 3
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 3
- 239000011737 fluorine Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 32
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 claims description 28
- 229960001867 guaiacol Drugs 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 12
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 8
- 230000002194 synthesizing effect Effects 0.000 claims description 7
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- 238000005886 esterification reaction Methods 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 4
- 150000004820 halides Chemical class 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- UCPYLLCMEDAXFR-UHFFFAOYSA-N triphosgene Chemical compound ClC(Cl)(Cl)OC(=O)OC(Cl)(Cl)Cl UCPYLLCMEDAXFR-UHFFFAOYSA-N 0.000 claims description 3
- VUGZANHKHAQMRE-UHFFFAOYSA-N (2-methoxyphenyl) hydrogen carbonate Chemical group COC1=CC=CC=C1OC(O)=O VUGZANHKHAQMRE-UHFFFAOYSA-N 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 230000003301 hydrolyzing effect Effects 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 238000001259 photo etching Methods 0.000 abstract description 4
- 238000009792 diffusion process Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 238000010189 synthetic method Methods 0.000 abstract 1
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 30
- 239000000243 solution Substances 0.000 description 26
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 24
- 239000000543 intermediate Substances 0.000 description 19
- 238000003756 stirring Methods 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 229920002120 photoresistant polymer Polymers 0.000 description 8
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 238000011161 development Methods 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000012043 crude product Substances 0.000 description 6
- KJIFKLIQANRMOU-UHFFFAOYSA-N oxidanium;4-methylbenzenesulfonate Chemical compound O.CC1=CC=C(S(O)(=O)=O)C=C1 KJIFKLIQANRMOU-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 5
- 238000001459 lithography Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000000206 photolithography Methods 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000002390 rotary evaporation Methods 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- ZEEBGORNQSEQBE-UHFFFAOYSA-N [2-(3-phenylphenoxy)-6-(trifluoromethyl)pyridin-4-yl]methanamine Chemical compound C1(=CC(=CC=C1)OC1=NC(=CC(=C1)CN)C(F)(F)F)C1=CC=CC=C1 ZEEBGORNQSEQBE-UHFFFAOYSA-N 0.000 description 2
- 238000010009 beating Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- WPIRVUXAMPRMAY-UHFFFAOYSA-N cyclohexa-1,5-dien-1-yloxy(trimethyl)silane Chemical compound C[Si](C)(C)OC1=CCCC=C1 WPIRVUXAMPRMAY-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- PQJJJMRNHATNKG-UHFFFAOYSA-N ethyl bromoacetate Chemical compound CCOC(=O)CBr PQJJJMRNHATNKG-UHFFFAOYSA-N 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- GQJCAQADCPTHKN-UHFFFAOYSA-N methyl 2,2-difluoro-2-fluorosulfonylacetate Chemical compound COC(=O)C(F)(F)S(F)(=O)=O GQJCAQADCPTHKN-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- LZKVGVXWGQWLAI-UHFFFAOYSA-M sodium;1,1-difluoro-2-hydroxyethanesulfonate Chemical compound [Na+].OCC(F)(F)S([O-])(=O)=O LZKVGVXWGQWLAI-UHFFFAOYSA-M 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
- C07D333/08—Hydrogen atoms or radicals containing only hydrogen and carbon atoms
- C07D333/10—Thiophene
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
- C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C309/07—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing oxygen atoms bound to the carbon skeleton
- C07C309/12—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing oxygen atoms bound to the carbon skeleton containing esterified hydroxy groups bound to the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
- C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C309/17—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing carboxyl groups bound to the carbon skeleton
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
- C07C2602/14—All rings being cycloaliphatic
- C07C2602/26—All rings being cycloaliphatic the ring system containing ten carbon atoms
- C07C2602/30—Azulenes; Hydrogenated azulenes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a sulfonium sulfonate photo-acid generator synthesized by guaiol and a synthesis method thereof, belonging to the field of chemical synthesis and photoetching materials. The general structural formula of the photoacid generator is as follows:
in the formula, R1Is composed of
And
one of (1); r2Is one of a covalent bond, an alkyl group, a cycloalkyl group, an ester group-containing alkyl group and a fluorine-containing alkyl group. The synthetic method of the photoacid generator comprises the following steps: guaiol reacts with a sulfonate compound to obtain an intermediate; and (2) reacting the intermediate with (cyclohexyl-1, 5-dialkenyloxy) -trimethyl-silane, tetramethylene sulfoxide and trifluoroacetic anhydride to obtain the sulfonium sulfonate photo-acid generator. The guaiol used as the raw material has higher molecular weight, and the formed photoacid generator also has higher molecular weight, so that the diffusion of the photoacid generator can be reduced, the improvement of edge roughness is facilitated, the line width roughness is reduced, and the resolution is improved.
Description
Technical Field
The invention relates to the field of chemical synthesis and photoetching materials, in particular to a sulfonium sulfonate photo-acid generator synthesized by guaiol and a synthesis method 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 development of the lithography technology is not independent of the development of the lithography material, and the development of the lithography material determines the development and application of the lithography technology to a certain extent. The photolithography material (specifically referred to as photoresist), also called photoresist, is the most critical functional chemical material involved in photolithography technology, and its main components are resin, Photo Acid Generator (PAG), and corresponding additives and solvents. The photoacid generator is a photosensitive compound, which decomposes under light irradiation to generate an acid, which can decompose or crosslink the acid-sensitive resin, thereby increasing the dissolution contrast between the irradiated part and the non-irradiated part in a developer, and can be used in the technical field of pattern microfabrication.
With the development of large-scale and ultra-large-scale integrated circuits in recent years, the research, development and application of photoresist are greatly promoted. As the feature size of integrated circuits decreases, the effect of edge roughness becomes more pronounced and the types of photoacid generators are developed. However, the conventional photoacid generator still has a problem of diffusion of acid, and thus edge roughness cannot be reduced.
Disclosure of Invention
An object of the embodiments of the present invention is to provide a sulfonium sulfonate photoacid generator synthesized from guaiacol, which solves the above problems of the background art.
In order to achieve the above purpose, the embodiments of the present invention provide the following technical solutions:
the sulfonic sulfonium salt photoacid generator synthesized from guaiol has a general structural formula as shown in formula I:
in the formula, R1Is composed of
And
one of (1); r2Is one of a covalent bond, an alkyl group, a cycloalkyl group, an ester group-containing alkyl group and a fluorine-containing alkyl group.
As a preferred embodiment of the present invention, the structural formula of the sulfonium sulfonate salt photoacid generator is one of formula II, formula III and formula IV:
another object of the embodiments of the present invention is to provide a method for synthesizing the above sulfonium sulfonate photoacid generator, which comprises the following steps:
guaiol reacts with a sulfonate compound to obtain an intermediate;
and (2) reacting the intermediate with (cyclohexyl-1, 5-dialkenyloxy) -trimethyl-silane, tetramethylene sulfoxide and trifluoroacetic anhydride to obtain the sulfonium sulfonate photo-acid generator.
As another preferable mode of the embodiment of the present invention, the sulfonate compound is a carboxyl group-containing sulfonate; the step of reacting guaiol with a sulfonate compound to obtain an intermediate specifically comprises:
carrying out esterification reaction on guaiol and sulfonate containing carboxyl to obtain an intermediate; the intermediate is sulfonate containing guaiacol ester group.
Wherein R in the formula of the sulfonic sulfonium salt type photoacid generator obtained by the technical scheme1Is composed of
As another preferable mode of the embodiment of the present invention, the sulfonate compound is a hydroxyl group-containing sulfonate; the step of reacting guaiol with a sulfonate compound to obtain an intermediate specifically comprises:
guaiol reacts with sulfonate containing hydroxyl to obtain an intermediate; the intermediate is sulfonate containing guaiacol carbonate group.
Wherein R in the formula of the sulfonic sulfonium salt type photoacid generator obtained by the technical scheme1Is composed of
As another preferable mode of the embodiment of the present invention, the sulfonate compound is a hydroxyl group-containing sulfonate; the step of reacting guaiol with a sulfonate compound to obtain an intermediate specifically comprises:
guaiol reacts with ester-group-containing halide to obtain ester-group-containing ether compounds;
hydrolyzing the ester group of the ether compound containing the ester group under an alkaline condition, and adjusting the ester group to be acidic to obtain an ether compound containing a carboxyl group;
carrying out esterification reaction on the ether compound containing carboxyl and sulfonate containing hydroxyl to obtain an intermediate; the intermediate is sulfonate containing ester group.
Wherein R in the formula of the sulfonic sulfonium salt type photoacid generator obtained by the technical scheme1Is composed of
In another preferable embodiment of the present invention, the sulfonate compound is one of a sodium sulfonate compound, a potassium sulfonate compound, and a lithium sulfonate compound.
As another preferable mode of the embodiment of the present invention, p-toluenesulfonic acid is used as a catalyst in the esterification reaction.
As another preferable embodiment of the present invention, the step of reacting guaiol with a hydroxyl group-containing sulfonate to obtain an intermediate specifically includes:
guaiol and sulfonate containing hydroxyl are put in a system containing pyridine and bis (trichloromethyl) carbonate for reaction to obtain an intermediate.
As another preferable mode of the embodiment of the present invention, the ester group-containing halide is an ester group-containing bromide.
Another object of the embodiments of the present invention is to provide a use of the above sulfonium sulfonate photoacid generator synthesized from guaiacol in a lithography material.
Compared with the prior art, the embodiment of the invention has the beneficial effects that:
(1) the synthetic raw material guaiacol adopted by the sulfonium sulfonate photoacid generator provided by the embodiment of the invention has higher molecular weight, and the formed photoacid generator also has higher molecular weight, so that the exposure and postbaking processes of photoetching and the diffusion of acid generated in an exposure area are reduced, the edge roughness of a photoetching pattern is favorably improved, the line width roughness is reduced, and the pattern resolution is improved.
(2) The sulfonium sulfonate photoacid generator provided by the embodiment of the invention contains an ester group, so that the lipid solubility of the photoacid generator can be increased, the photoacid generator is more easily dissolved in a solvent, the polarity of the photoacid generator and resin is closer, the resin and the photoacid generator are more uniformly mixed in the solvent, and the formation of more uniform photoresist is facilitated.
(3) The sulfonium sulfonate photo-acid generator provided by the embodiment of the invention contains aliphatic rings, and has excellent etching resistance.
(4) The sulfonium sulfonate photo-acid generator provided by the embodiment of the invention has the advantages of simple and easily available raw materials, simple synthetic route and convenience for preparation and generation.
(5) The sulfonium sulfonate photo-acid generator provided by the embodiment of the invention does not contain benzene rings, has better transparency at 193nm, and has less influence on the transparency of 193nm photoresist when the 193nm photoresist is formed by doping, thereby being beneficial to better exposure of the photoresist.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to 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. 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.
Example 1
This example provides a sulfonium sulfonate photoacid generator synthesized from guaiacol, the reaction scheme of the synthesis method of the photoacid generator is as follows:
the method specifically comprises the following steps:
s1, dissolving sodium hydroxide (7g, 175mmol) in water (17g) to prepare a 30% sodium hydroxide solution; adding 1-1(10g, 52mmol) of methyl fluorosulfonyl difluoroacetate into ice water (33g) to obtain a reaction solution, slowly adding a prepared 30% sodium hydroxide solution into the reaction solution under stirring, stirring the reaction solution in an ice bath (the temperature is controlled to be lower than 10 ℃) for 2.5 hours after the addition is finished, then continuing stirring at room temperature for 1 hour, starting heating until the temperature rises to 95 ℃ within 30 minutes, stirring at 95 ℃ for 3 hours, stopping heating, cooling to room temperature, neutralizing with hydrochloric acid, filtering the reaction solution, collecting a filtrate, adding acetone (600g) into the filtrate, precipitating a white solid, filtering, washing a filter cake with acetone (60g), and drying to obtain a compound 1-2(11g, 50mmol, 96% yield).
S2, compound 1-2(11g, 50mmol) was added to acetonitrile (150g), p-toluenesulfonic acid monohydrate (14.6g, 77mmol) was added thereto, and the mixture was stirred at room temperature for 30 minutes to obtain a reaction solution, and then the reaction solution was heated to 80 degrees celsius, and after stirring at 80 degrees celsius for 3 hours, the reaction solution was cooled to room temperature, filtered, and the filter cake was dried to obtain compound 1-3(7.6g, 38mmol, yield 77%) as a white solid.
S3, adding the compound 1-3(7.6g, 38mmol), guaiacol (8.6g, 39mmol) and p-toluenesulfonic acid monohydrate (1.1g, 5.8mmol) to 250g of toluene to obtain a reaction solution, heating and refluxing the reaction solution for 18 hours, and cooling to room temperature to obtain a mixture; then, the mixture was filtered to obtain a solid, the solid was washed three times with acetonitrile (150 × 3), an acetonitrile solution was collected, the collected acetonitrile solution was concentrated and added to methyl t-butyl ether (100g) to carry out beating to obtain a mixed solution, the above mixed solution was filtered, and the cake was collected and dried to obtain intermediates 1 to 4(14g, 35mmol, yield 90.7%) as a solid.
S4, (cyclohexyl-1, 5-dialkenyloxy) -trimethyl-silane (6g, 36mmol) and tetramethylene sulfoxide (3.7g, 36mmol) are dissolved in chloroform (300g) under the protection of nitrogen flow and cooled to-30 ℃, then trifluoroacetic anhydride (11g, 52mmol) is slowly added within 30 minutes, after stirring for reaction for 30 minutes, a saturated aqueous solution of the above intermediates 1-4(14g, 35mmol) is further added with stirring and stirring for reaction for 1 hour, after the reaction is finished, the temperature is returned to room temperature, water and chloroform are separated, the aqueous phase is extracted 3 times with chloroform (80g × 3), the chloroform phase is concentrated under vacuum to obtain a crude product, and the crude product is washed with diisopropyl ether to obtain sulfonic sulfonium salt photoacid generator 1-5(15g, 27mmol, 77%) yield.
Example 2
This example provides a sulfonium sulfonate photoacid generator synthesized from guaiacol, the reaction scheme of the synthesis method of the photoacid generator is as follows:
the method specifically comprises the following steps:
s1, under the protection of nitrogen at 0 ℃, adding pyridine (9g, 114mmol) and bis (trichloromethyl) carbonate (4.5g, 15mmol) into dichloromethane (300g), and slowly adding guaiacol 2-1(10g, 45mmol) under stirring to obtain a reaction solution; next, the reaction solution was left at room temperature and stirred for 3 hours, then 1, 1-difluoro-2-hydroxy-ethanesulfonic acid sodium salt (8.8g, 48mmol) was added to the reaction solution, stirred for 10 hours, the reaction solution was concentrated under vacuum to give a mixture, the mixture was filtered to give a solid, the solid was washed with acetonitrile (150g × 3) three times, the acetonitrile solution was collected, the collected acetonitrile solution was concentrated and added to methyl tert-butyl ether (100g) for beating to give a mixed solution, the above mixed solution was filtered, and the oven-dried cake was collected to give intermediate 2-2(14.8g, 34mmol, yield 76%) as a solid.
S2, (cyclohexa-1, 5-dienyloxy) -trimethyl-silane (5.8g, 34mm ol) and tetramethylene sulfoxide (3.6g, 34mmol) were dissolved in chloroform (320g) under nitrogen flow and cooled to-30 ℃, then trifluoroacetic anhydride (11g, 52mmol) was slowly added over 30 minutes, after stirring for reaction for 30 minutes, a saturated aqueous solution of the above intermediate 2-2(14.8g, 34mmol) was further added with stirring and reaction was carried out for 1 hour with stirring, after the reaction was over, the temperature was returned to room temperature, water and chloroform were separated, the aqueous phase was extracted with chloroform, the chloroform phase was concentrated under vacuum to give a crude product, which was washed with methyl tert-butyl ether and dried to give the sulfoniumsulfonate photoacid generator 2-3(16g, 27mmol, 79% yield).
Example 3
This example provides a sulfonium sulfonate photoacid generator synthesized from guaiacol, the reaction scheme of the synthesis method of the photoacid generator is as follows:
the method specifically comprises the following steps:
s1, slowly adding sodium hydride (1.3g, 54mmol) to a mixture of guaiacol 3-1(10g, 45mmol) and anhydrous tetrahydrofuran (200g) at 0 ℃ under nitrogen, and stirring for 20 minutes; ethyl bromoacetate (8g, 48mmol) was then added dropwise to the above mixture, and the mixture was stirred for 20 minutes; then, the reaction was carried out by stirring at 25 ℃ for 6 hours, and after completion of the reaction, water was added thereto to quench at 0 ℃. Concentrating the quenched mixed solution by rotary evaporation, extracting with dichloromethane (150g multiplied by 3) for three times, combining the extracts, washing the separated liquid with saturated saline solution (100g), drying with anhydrous sodium sulfate, and concentrating by rotary evaporation to obtain a crude product; the crude product was purified by column chromatography to give compound 3-2(12.6g, 41mmol, 91% yield).
S2, adding the compound 3-2(12.6g, 41mmol) and sodium hydroxide (2.5g, 63mmol) into a mixed solution of water (10g) and methanol (40g), and stirring at 25 ℃ for 24h to obtain a reaction solution; then, concentrating the reaction solution, and adjusting the pH value of the reaction solution to 2 by using hydrochloric acid to obtain a mixed solution; then, the resulting mixture was extracted twice with ethyl acetate (150g × 3), the extracts were combined and washed with saturated brine (100g), and then dried over anhydrous sodium sulfate, followed by rotary evaporation and concentration to obtain compound 3-3(9.8g, 35mmol, yield 86%) as a liquid.
S3, compound 3-3(9.8g, 35mmol), 1-difluoro-2-hydroxy-ethanesulfonic acid sodium salt (6.5g, 35mmol) and p-toluenesulfonic acid monohydrate (1.0g, 5.3mmol) were added to toluene (500g), and after heating to reflux for 18 hours, cooling to room temperature again gave a mixture. Subsequently, the mixture was filtered to obtain a solid, which was washed three times with acetonitrile, and the acetonitrile solution was collected. The collected acetonitrile solution was concentrated and added to methyl t-butyl ether for pulping, the above mixture was filtered, and the dried cake was collected to obtain intermediate 3-4(13.6g, 30mmol, yield 87%) as a solid.
S4, (cyclohexa-1, 5-dienyloxy) -trimethyl-silane (5.2g, 31 mm. ol) and tetramethylene sulfoxide (3.2g, 31mmol) were dissolved in chloroform (280g) under nitrogen flow and cooled to-30 ℃, then trifluoroacetic anhydride (9.6g, 46mmol) was slowly added over 30 minutes, after stirring for reaction for 30 minutes, a saturated aqueous solution of the above intermediate 3-4(13.6g, 30mmol) was further added with stirring and reaction was carried out for 1 hour with stirring, after the reaction was over, room temperature was returned to room temperature, water and chloroform were separated, the aqueous phase was extracted with chloroform, the chloroform phase was concentrated under vacuum to give a crude product, which was washed with methyl t-butyl ether and dried to give 3-5(15g, 25mmol, yield 80.5%) of a sulfonium sulfonate photoacid generator.
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.
Claims (10)
1. The sulfonium sulfonate photoacid generator synthesized from guaiol is characterized in that the structural general formula of the sulfonium sulfonate photoacid generator is shown as formula I:
in the formula, R1Is composed of
One of (1); r2Is one of a covalent bond, an alkyl group, a cycloalkyl group, an ester group-containing alkyl group and a fluorine-containing alkyl group.
2. The sulfonium sulfonate photoacid generator synthesized from guaiacol as claimed in claim 1, wherein the sulfonium sulfonate photoacid generator has a structural formula of one of formula II, formula III and formula IV:
3. a method for synthesizing a sulfonium sulfonate photoacid generator synthesized from guaiol as claimed in any one of claims 1 to 2, comprising the steps of:
guaiol reacts with a sulfonate compound to obtain an intermediate;
and (2) reacting the intermediate with (cyclohexyl-1, 5-dialkenyloxy) -trimethyl-silane, tetramethylene sulfoxide and trifluoroacetic anhydride to obtain the sulfonium sulfonate photo-acid generator.
4. The method for synthesizing a sulfonium sulfonate photoacid generator synthesized from guaiacol as claimed in claim 3, wherein the sulfonate compound is a carboxyl group-containing sulfonate; the step of reacting guaiol with a sulfonate compound to obtain an intermediate specifically comprises:
carrying out esterification reaction on guaiol and sulfonate containing carboxyl to obtain an intermediate; the intermediate is sulfonate containing guaiacol ester group.
5. The method for synthesizing a sulfonium sulfonate photoacid generator synthesized from guaiacol as claimed in claim 3, wherein the sulfonate compound is a hydroxyl group-containing sulfonate; the step of reacting guaiol with a sulfonate compound to obtain an intermediate specifically comprises:
guaiol reacts with sulfonate containing hydroxyl to obtain an intermediate; the intermediate is sulfonate containing guaiacol carbonate group.
6. The method for synthesizing a sulfonium sulfonate photoacid generator synthesized from guaiacol as claimed in claim 3, wherein the sulfonate compound is a hydroxyl group-containing sulfonate; the step of reacting guaiol with a sulfonate compound to obtain an intermediate specifically comprises:
guaiol reacts with ester-group-containing halide to obtain ester-group-containing ether compounds;
hydrolyzing the ester group of the ether compound containing the ester group under an alkaline condition, and adjusting the ester group to be acidic to obtain an ether compound containing a carboxyl group;
carrying out esterification reaction on the ether compound containing carboxyl and sulfonate containing hydroxyl to obtain an intermediate; the intermediate is sulfonate containing ester group.
7. The method for synthesizing a sulfonium sulfonate photoacid generator from guaiol according to any of claims 4 to 6, wherein the sulfonate compound is one of a sodium sulfonate compound, a potassium sulfonate compound and a lithium sulfonate compound.
8. The method for synthesizing a sulfonium sulfonate photoacid generator as claimed in claim 4 or 6, wherein p-toluenesulfonic acid is used as a catalyst in the esterification reaction.
9. The method as claimed in claim 5, wherein the step of reacting guaiol with hydroxyl group-containing sulfonate to obtain an intermediate comprises:
guaiol and sulfonate containing hydroxyl are put in a system containing pyridine and bis (trichloromethyl) carbonate for reaction to obtain an intermediate.
10. Use of the sulfonium sulfonate photoacid generator of any of claims 1-2 in a lithographic material.
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