CN111675680A - Trifluoro sulfonamide pyran type photoresist resin monomer and preparation method thereof - Google Patents
Trifluoro sulfonamide pyran type photoresist resin monomer and preparation method thereof Download PDFInfo
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- CN111675680A CN111675680A CN202010550524.3A CN202010550524A CN111675680A CN 111675680 A CN111675680 A CN 111675680A CN 202010550524 A CN202010550524 A CN 202010550524A CN 111675680 A CN111675680 A CN 111675680A
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- resin monomer
- compound
- pyran
- photoresist resin
- trifluorosulfonamide
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- 239000011347 resin Substances 0.000 title claims abstract description 36
- 229920005989 resin Polymers 0.000 title claims abstract description 36
- 239000000178 monomer Substances 0.000 title claims abstract description 34
- 229920002120 photoresistant polymer Polymers 0.000 title claims abstract description 32
- YMOSRKSHQMSXRE-UHFFFAOYSA-N O1CC=CC=C1.FN(S(=O)(=O)F)F Chemical compound O1CC=CC=C1.FN(S(=O)(=O)F)F YMOSRKSHQMSXRE-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- -1 amino pyranol compound Chemical class 0.000 claims abstract description 29
- 150000001875 compounds Chemical class 0.000 claims abstract description 17
- 239000003513 alkali Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000001257 hydrogen Substances 0.000 claims abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 7
- 125000004404 heteroalkyl group Chemical group 0.000 claims abstract description 5
- 239000011259 mixed solution Substances 0.000 claims abstract description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical class OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000005886 esterification reaction Methods 0.000 claims abstract description 3
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 3
- 150000002367 halogens Chemical class 0.000 claims abstract description 3
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- WJKHJLXJJJATHN-UHFFFAOYSA-N triflic anhydride Chemical compound FC(F)(F)S(=O)(=O)OS(=O)(=O)C(F)(F)F WJKHJLXJJJATHN-UHFFFAOYSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- DCUFMVPCXCSVNP-UHFFFAOYSA-N methacrylic anhydride Chemical compound CC(=C)C(=O)OC(=O)C(C)=C DCUFMVPCXCSVNP-UHFFFAOYSA-N 0.000 claims description 4
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 claims description 3
- GRGCWBWNLSTIEN-UHFFFAOYSA-N trifluoromethanesulfonyl chloride Chemical compound FC(F)(F)S(Cl)(=O)=O GRGCWBWNLSTIEN-UHFFFAOYSA-N 0.000 claims description 3
- SLVAEVYIJHDKRO-UHFFFAOYSA-N trifluoromethanesulfonyl fluoride Chemical compound FC(F)(F)S(F)(=O)=O SLVAEVYIJHDKRO-UHFFFAOYSA-N 0.000 claims description 3
- UDSNIGGFYHWMEH-UHFFFAOYSA-N 3-amino-2h-pyran-2-ol Chemical class NC1=CC=COC1O UDSNIGGFYHWMEH-UHFFFAOYSA-N 0.000 claims description 2
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 claims description 2
- ARJOQCYCJMAIFR-UHFFFAOYSA-N prop-2-enoyl prop-2-enoate Chemical compound C=CC(=O)OC(=O)C=C ARJOQCYCJMAIFR-UHFFFAOYSA-N 0.000 claims description 2
- 239000002585 base Substances 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 4
- MGADZUXDNSDTHW-UHFFFAOYSA-N 2H-pyran Chemical compound C1OC=CC=C1 MGADZUXDNSDTHW-UHFFFAOYSA-N 0.000 abstract 1
- 230000002579 anti-swelling effect Effects 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- USPTVMVRNZEXCP-UHFFFAOYSA-N sulfamoyl fluoride Chemical compound NS(F)(=O)=O USPTVMVRNZEXCP-UHFFFAOYSA-N 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 238000001459 lithography Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000012074 organic phase Substances 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000005530 etching Methods 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000003480 eluent Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- SXKLNBJCHYEPDL-UHFFFAOYSA-N n,n-difluorosulfamoyl fluoride Chemical group FN(F)S(F)(=O)=O SXKLNBJCHYEPDL-UHFFFAOYSA-N 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000010898 silica gel chromatography Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- SCCVKSIEMVHVOG-UHFFFAOYSA-N 5-aminooxan-3-ol Chemical compound NC1COCC(O)C1 SCCVKSIEMVHVOG-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- LGXUYQPVNUGLTG-RITPCOANSA-N [(2s,5r)-5-aminooxan-2-yl]methanol Chemical compound N[C@@H]1CC[C@@H](CO)OC1 LGXUYQPVNUGLTG-RITPCOANSA-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
- 125000004429 atom Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 229940098779 methanesulfonic acid Drugs 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000000206 photolithography Methods 0.000 description 2
- 125000004309 pyranyl group Chemical group O1C(C=CC=C1)* 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229940124530 sulfonamide Drugs 0.000 description 2
- 150000003456 sulfonamides Chemical class 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N tert-butyl alcohol Substances CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- IDBYQQQHBYGLEQ-UHFFFAOYSA-N 1,1,2,2,3,3,4-heptafluorocyclopentane Chemical compound FC1CC(F)(F)C(F)(F)C1(F)F IDBYQQQHBYGLEQ-UHFFFAOYSA-N 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- XHFLOLLMZOTPSM-UHFFFAOYSA-M sodium;hydrogen carbonate;hydrate Chemical class [OH-].[Na+].OC(O)=O XHFLOLLMZOTPSM-UHFFFAOYSA-M 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
- C07D309/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D309/08—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D309/14—Nitrogen atoms not forming part of a nitro radical
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
- C07D309/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D309/04—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
- C07D309/06—Radicals substituted by oxygen atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a trifluoro sulfonamide pyran type photoresist resin monomer and a preparation method thereof, wherein the trifluoro sulfonamide pyran type photoresist resin monomer comprises the following structural general formula:
wherein R is1And R2Respectively comprise C1～C12Alkyl, heteroalkyl, or a linkage; r3Including hydrogen, halogen, C1～C12Alkyl or heteroalkyl, a process for its preparation, comprising the steps of: adding a trifluorosulfonyl compound into a mixed solution of an amino pyranol compound and an alkali, and reacting to obtain a trifluorosulfonamide pyranol compound; and mixing the trifluoro sulfonamide pyranyl compounds with acrylic acid compounds, and purifying to obtain the trifluoro sulfonamide pyranyl photoresist resin monomer through esterification reaction. Synthesis of IIIThe fluorosulfonamide pyran photoresist resin monomer has the advantages of anti-swelling property, alkali solubility and hydrophobicity, and the preparation method is simple and convenient.
Description
Technical Field
The invention relates to the technical field of photoresist, in particular to a trifluoro sulfonamide pyran type photoresist resin monomer and a preparation method thereof.
Background
Lithography (Lithography) refers to a fine processing technique for transferring a pattern designed on a Mask (Mask) to a pattern on a substrate by using the chemical sensitivity of a Lithography material (particularly a photoresist) under the action of visible light, ultraviolet light, an electron beam 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 lithography technology goes through the development process of the next generation lithography technologies, such as G-line (436nm) and I-line (365nm) near ultraviolet optical lithography, deep ultraviolet (248nm and 193nm) and vacuum ultraviolet (157nm) optical lithography, extreme ultraviolet (13.5nm), electron beam, nanoimprint, block copolymer self-assembly, scanning probe and the like, and is now an essential and important process for manufacturing large-scale integrated circuits and very large-scale integrated circuits.
In 193nm immersion (193i) lithography, the photoresist is exposed by immersion in water. This puts some special requirements on 193i photoresist. First, the active ingredients of the photoresist must be insoluble in water; the chemical properties of the photoresist do not change after contact with water; second, the photoresist must be somewhat resistant to water, and diffusion of water into the photoresist does not result in swelling of the colloid and loss of photosensitivity.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects of the prior art, and provide a trifluoro sulfonamide pyran type photoresist resin monomer with better alkali solubility and etching resistance, and a corresponding preparation method is another object of the invention.
In order to solve the technical problems, the invention provides the following technical scheme:
the invention relates to a trifluoro sulfonamide pyran type photoresist resin monomer, which comprises the following structural general formula:
wherein R is1And R2Respectively comprise C1～C12Alkyl, heteroalkylOr a connecting bond; r3Including hydrogen, halogen, C1～C12Alkyl or heteroalkyl.
As a preferable technical means of the present invention, R is1And R2Respectively comprise C1～C6Alkyl or a connecting bond, said R3Including hydrogen or C1～C6An alkyl group.
As a preferred embodiment of the present invention, the resin monomer comprises the following structure:
The preparation method of the trifluoro sulfonamide pyran photoresist resin monomer comprises the following steps:
s1, adding the trifluorosulfonyl compounds into the mixed solution of the aminopyranols compounds and the alkali, and reacting to obtain the trifluorosulfonamide pyranols compounds;
and S2, mixing the trifluoro sulfonamide pyranyl alcohol compound with an acrylic acid compound, and purifying to obtain the trifluoro sulfonamide pyranyl photoresist resin monomer through an esterification reaction.
As a preferable technical scheme of the invention, the molar ratio of the aminopyranols compound to the trifluorosulfonyl compound is 1 (1-1.5), and the molar ratio of the trifluorosulfonyl compound to the alkali is 1 (1-3); the molar ratio of the trifluoro sulfonamide pyranol compound to the acrylic compound is 1: (0.9-1).
As a preferable technical scheme of the invention, the molar ratio of the aminopyranols compound to the trifluoromethanesulfonyl compound to the alkali is 1:1: 1.5; the molar ratio of the trifluoro sulfonamide pyranol compound to the acrylic compound is 1:1.
in a preferred embodiment of the present invention, in S1, the aminopyranols compound has the following structure:
as a preferable technical solution of the present invention, in S1, the trifluorosulfonyl compound includes one of trifluoromethane sulfonyl chloride, trifluoromethane sulfonyl fluoride, or trifluoromethane sulfonic anhydride.
In a preferred embodiment of the present invention, in S2, the acrylic compound includes one of acrylic anhydride, acryloyl chloride, methacrylic anhydride, and methacryloyl chloride.
Compared with the prior art, the invention has the following beneficial effects:
(1) the triflurosulfonamide structure has high transparency at 193nm, has a lower pKa value compared with hexafluoro-tert-butyl alcohol, and has a pKa value of 6-7, wherein the sulfonamide (-SO)2N on NH-) is subjected to electron-withdrawing effect of 2O atoms on S, the electron cloud density is small, the covalent bond bonding force between H is weak, and H becomes active H which is easy to dissociate, so that the main resin monomer containing the trifluorosulfonamide group has better alkali solubility; and the fluorine content is less, so that the main resin monomer containing the trifluorosulfonamide group has better etching resistance.
(2) The invention has pyran ring structure, which further increases the etching resistance of the resin.
(3) The preparation method is simple and convenient.
Detailed Description
The present invention will be further described with reference to specific examples, which are intended to illustrate and explain the present invention, but are not intended to limit the present invention.
Example 1
The trifluoro sulfonamide pyran type photoresist resin monomer prepared by taking 5-aminotetrahydro-2H-pyran-3-ol as a raw material has the following structure:
the preparation method of the resin monomer comprises the following steps:
s1, trifluoromethanesulfonyl chloride (86.0mmol, 14.5g) was added dropwise to a solution of 5-aminotetrahydro-2H-pyran-3-ol 1-1(85.4mmol, 10g) and triethylamine (128.5mmol, 13g) in acetonitrile (200g) at 0-4 ℃, followed by stirring at 10 ℃ for 1 hour. Distilling the above reaction solution under reduced pressure, adding the obtained residue into dipropyl ether, filtering, washing the filtrate with 10% sodium chloride three times, drying with anhydrous magnesium sulfate, concentrating, and subjecting the concentrate to silica gel column chromatography (MeOH/CH)2Cl21/10 as eluent) to give compound 1-2(40.1mmol, 10g, 47.0% yield).
S2, Compound 1-2(40.1mmol, 10g), methacrylic anhydride (42.2mmol, 6.5g) and toluene (20g) were charged into a four-necked flask. Methanesulfonic acid (10.4mmol, 1g) was then added dropwise and stirred at 50 ℃ for 5 hours. The reaction solution was filtered, and the obtained cake was dissolved in toluene (10g) and ethyl acetate (10g), washed with 6% aqueous sodium hydroxide solution and washed 3 times with water; drying the obtained organic phase with anhydrous magnesium sulfate, filtering, cooling the filtrate to-20 deg.C, and crystallizing to obtain off-white solid compound
1-3(26.8mmol, 8.5g, 66.8% yield).
Example 2
The trifluoro sulfonamide pyran type photoresist resin monomer prepared by taking ((2S, 5R) -5-aminotetrahydro-2H-pyran-2-yl) methanol as a raw material has the following specific structure:
the preparation method of the resin monomer comprises the following steps:
s1 preparation of ((2S, 5R) -5-aminotetrahydro-2H-pyran-2-yl) methanol 2-1(76.2mmol, 10g) andtriethylamine (113.6mmol, 11.5g) was dissolved in a mixed solution of acetonitrile (20g) and heptafluorocyclopentane (20g), and trifluoromethanesulfonyl fluoride (75.6mmol, 11.5g) gas was introduced at 0 ℃ and stirred for 1 hour. Water (30g) was added to the reaction solution, and the mixture was stirred for 30 minutes to obtain an organic phase. The organic phase was washed with 5% aqueous sulfuric acid and 5% aqueous sodium bicarbonate in that order and concentrated to give a residue. The residue was subjected to silica gel column chromatography (MeOH/CH)2Cl21/10 as eluent) to give compound 2-2(36.1mmol, 9.5g, 47.3% yield);
s2, acryloyl chloride (36.5mmol, 3.3g) was added dropwise to a mixture of compound 2-2(36.1mmol, 9.5g) and triethylamine (5.26mmol, 1g) in dichloromethane (120g) at 0 ℃ under nitrogen, and the mixture was stirred for 8 hours. Then dropwise adding saturated sodium bicarbonate water solution, separating to obtain an organic phase, sequentially washing the obtained organic phase with saturated saline solution, drying with anhydrous sodium sulfate and concentrating; the concentrate was chromatographed on silica gel column (MeOH/CH)2Cl21/20 as eluent) to give compound 2-3 as an off-white solid (26.8mmol, 8.5g, 74.2% yield).
Example 3
The trifluoro sulfonamide pyran type photoresist resin monomer prepared by 1- (4-aminomethyl-tetrahydro-pyran-4-yl) -2-methoxyl-ethanol has the following structure:
the preparation method of the resin monomer comprises the following steps:
s1 trifluoromethanesulfonic anhydride (53.2mmol, 15g) was added dropwise to a solution of 1- (4-aminomethyl-tetrahydro-pyran-4-yl) -2-methoxy-ethanol 3-1(52.8mmol, 10g) and triethylamine (79.1mmol, 8g) in acetonitrile (200g) at-30 ℃ and stirred for 1 h. Distilling the reaction liquid under reduced pressure to obtain a residue, and adding the residue into dipropyl ether; filtering, the filtrate is 10%Washed three times with sodium chloride, dried over anhydrous magnesium sulfate, concentrated, and the concentrate was subjected to silica gel column chromatography (MeOH/CH)2Cl21/10 as eluent) to give compound 3-2(31.1mol, 10g, 58.9% yield).
S2, Compound 3-2(31.1mol, 10g), methacrylic anhydride (32.4mmol, 5g) and toluene (20g) were charged into a four-necked flask. Methanesulfonic acid (10.4mmol, 1g) was then added and stirred at 50 ℃ for 5 hours. The reaction solution was filtered, the obtained cake was dissolved in toluene (10g) and ethyl acetate (10g), washed successively with 6% aqueous sodium hydroxide solution and 3 times with water to obtain an organic phase, the organic phase was dried over anhydrous magnesium sulfate, filtered and the filtrate was cooled to-20 ℃ to crystallize to obtain compound 3-3 as an off-white solid (21.8mmol, 8.5g, yield 70.1%).
Compared with the prior art, the invention has the following beneficial effects:
(1) the triflurosulfonamide structure has high transparency at 193nm, has a lower pKa value compared with hexafluoro-tert-butyl alcohol, and has a pKa value of 6-7, wherein the sulfonamide (-SO)2N on NH-) is subjected to electron-withdrawing effect of 2O atoms on S, the electron cloud density is small, the covalent bond bonding force between H is weak, and H becomes active H which is easy to dissociate, so that the main resin monomer containing the trifluorosulfonamide group has better alkali solubility; and the fluorine content is less, so that the main resin monomer containing the trifluorosulfonamide group has better etching resistance.
(2) The invention has pyran ring structure, which further increases the etching resistance of the resin.
(3) The preparation method is simple and convenient.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art will understand that various changes, modifications and substitutions can be made without departing from the spirit and scope of the invention as defined by the appended claims. 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 (9)
1. A trifluoro sulfonamide pyran based photoresist resin monomer is characterized in that the resin monomer comprises the following structural general formula:
wherein R is1And R2Respectively comprise C1～C12Alkyl, heteroalkyl, or a linkage; r3Including hydrogen, halogen, C1～C12Alkyl or heteroalkyl.
2. The trifluorosulfonamide pyran-based photoresist resin monomer of claim 1, wherein said R is1And R2Respectively comprise C1～C6Alkyl or a connecting bond, said R3Including hydrogen or C1～C6An alkyl group.
3. The trifluorosulfonamide pyran-based photoresist resin monomer of claim 2, wherein the resin monomer comprises the structure:
4. A method for preparing the trifluorosulfonamide pyran-based photoresist resin monomer according to any one of claims 1 to 3, comprising the steps of:
s1, adding the trifluorosulfonyl compounds into the mixed solution of the aminopyranols compounds and the alkali, and reacting to obtain the trifluorosulfonamide pyranols compounds;
and S2, mixing the trifluoro sulfonamide pyranyl alcohol compound with an acrylic acid compound, and purifying to obtain the trifluoro sulfonamide pyranyl photoresist resin monomer through an esterification reaction.
5. The preparation method of the trifluorosulfonamide pyran photoresist resin monomer according to claim 4, wherein the molar ratio of the aminopyranols compound to the trifluorosulfonyl compound is 1 (1-1.5), and the molar ratio of the trifluorosulfonyl compound to the alkali is 1 (1-3); the molar ratio of the trifluoro sulfonamide pyranol compound to the acrylic compound is 1: (0.9-1).
6. The method for preparing the trifluorosulfonamide pyran based photoresist resin monomer according to claim 5, wherein the molar ratio of the aminopyranols compound, the trifluorosulfonyl compound and the base is 1:1: 1.5; the molar ratio of the trifluoro sulfonamide pyranol to the acrylic compound is 1:1.
7. the method for preparing the trifluorosulfonamide pyran-based photoresist resin monomer according to claim 4, wherein in S1, the aminopyranols compound comprises the following structure:
8. the method for preparing the trifluorosulfonamide pyran-based photoresist resin monomer according to claim 4, wherein in S1, the trifluorosulfonyl compound comprises one of trifluoromethane sulfonyl chloride, trifluoromethane sulfonyl fluoride or trifluoromethane sulfonic anhydride.
9. The method for preparing the trifluorosulfonamide pyran-based photoresist resin monomer according to claim 4, wherein in S2, the acrylic compound comprises one of acrylic anhydride, acryloyl chloride, methacrylic anhydride, or methacryloyl chloride.
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| CN113416177A (en) * | 2021-06-24 | 2021-09-21 | 徐州博康信息化学品有限公司 | Main chain degradable photoresist resin monomer and preparation method and application thereof |
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| US20050003303A1 (en) * | 2003-06-12 | 2005-01-06 | Takeru Watanabe | Polymerizable ester having sulfonamide structure, polymer, resist composition and patterning process |
| JP2011252145A (en) * | 2010-05-06 | 2011-12-15 | Sumitomo Chemical Co Ltd | Polymer and resist composition |
| JP2013140268A (en) * | 2012-01-05 | 2013-07-18 | Shin Etsu Chem Co Ltd | Pattern forming method |
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| US20050003303A1 (en) * | 2003-06-12 | 2005-01-06 | Takeru Watanabe | Polymerizable ester having sulfonamide structure, polymer, resist composition and patterning process |
| JP2011252145A (en) * | 2010-05-06 | 2011-12-15 | Sumitomo Chemical Co Ltd | Polymer and resist composition |
| JP2013140268A (en) * | 2012-01-05 | 2013-07-18 | Shin Etsu Chem Co Ltd | Pattern forming method |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113416177A (en) * | 2021-06-24 | 2021-09-21 | 徐州博康信息化学品有限公司 | Main chain degradable photoresist resin monomer and preparation method and application thereof |
| CN113416177B (en) * | 2021-06-24 | 2022-10-25 | 徐州博康信息化学品有限公司 | Main chain degradable photoresist resin monomer and preparation method and application thereof |
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