CN113493382A - Photoresist acid-sensitive resin monomer with good alkali solubility and synthesis method and application thereof - Google Patents
Photoresist acid-sensitive resin monomer with good alkali solubility and synthesis method and application thereof Download PDFInfo
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- CN113493382A CN113493382A CN202110694962.1A CN202110694962A CN113493382A CN 113493382 A CN113493382 A CN 113493382A CN 202110694962 A CN202110694962 A CN 202110694962A CN 113493382 A CN113493382 A CN 113493382A
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- Prior art keywords
- photoresist
- acid
- resin monomer
- sensitive resin
- alkali solubility
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- 229920002120 photoresistant polymer Polymers 0.000 title claims abstract description 42
- 239000000178 monomer Substances 0.000 title claims abstract description 33
- 239000011347 resin Substances 0.000 title claims abstract description 33
- 229920005989 resin Polymers 0.000 title claims abstract description 33
- 239000002253 acid Substances 0.000 title claims abstract description 25
- 239000003513 alkali Substances 0.000 title claims abstract description 20
- 238000001308 synthesis method Methods 0.000 title abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 12
- 125000002723 alicyclic group Chemical group 0.000 claims abstract description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 5
- 239000001257 hydrogen Substances 0.000 claims abstract description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 5
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 48
- 239000000543 intermediate Substances 0.000 claims description 47
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 30
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000007810 chemical reaction solvent Substances 0.000 claims description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 150000003997 cyclic ketones Chemical class 0.000 claims description 10
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical group [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 8
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052736 halogen Inorganic materials 0.000 claims description 8
- 150000002367 halogens Chemical group 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- 239000012312 sodium hydride Substances 0.000 claims description 8
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 8
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 4
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 4
- 239000007800 oxidant agent Substances 0.000 claims description 4
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 3
- NHQDETIJWKXCTC-UHFFFAOYSA-N 3-chloroperbenzoic acid Chemical group OOC(=O)C1=CC=CC(Cl)=C1 NHQDETIJWKXCTC-UHFFFAOYSA-N 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims description 2
- 238000003747 Grignard reaction Methods 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 238000007259 addition reaction Methods 0.000 claims description 2
- RJUIDDKTATZJFE-UHFFFAOYSA-N but-2-enoyl chloride Chemical compound CC=CC(Cl)=O RJUIDDKTATZJFE-UHFFFAOYSA-N 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 150000002009 diols Chemical class 0.000 claims description 2
- 238000005886 esterification reaction Methods 0.000 claims description 2
- 125000001033 ether group Chemical group 0.000 claims description 2
- 230000003301 hydrolyzing effect Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 150000003509 tertiary alcohols Chemical group 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000005530 etching Methods 0.000 abstract description 2
- 239000012074 organic phase Substances 0.000 description 26
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 24
- 239000000243 solution Substances 0.000 description 21
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 17
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 14
- 238000001035 drying Methods 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 12
- 238000001816 cooling Methods 0.000 description 12
- 239000005457 ice water Substances 0.000 description 12
- 239000008346 aqueous phase Substances 0.000 description 11
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 238000003756 stirring Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 7
- 238000010791 quenching Methods 0.000 description 7
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- 229940102396 methyl bromide Drugs 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 4
- 230000000171 quenching effect Effects 0.000 description 4
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical class [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
- BZKFMUIJRXWWQK-UHFFFAOYSA-N Cyclopentenone Chemical compound O=C1CCC=C1 BZKFMUIJRXWWQK-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000001259 photo etching Methods 0.000 description 2
- 238000006552 photochemical reaction Methods 0.000 description 2
- 238000000206 photolithography Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- HUQXEIFQYCVOPD-UHFFFAOYSA-N bicyclo[2.2.1]hept-2-en-5-one Chemical compound C1C2C(=O)CC1C=C2 HUQXEIFQYCVOPD-UHFFFAOYSA-N 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000002373 hemiacetals Chemical class 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical group 0.000 description 1
- 150000002596 lactones Chemical group 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
- C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
- C07C69/54—Acrylic acid esters; Methacrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/63—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of halogen; by substitution of halogen atoms by other halogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/64—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of functional groups containing oxygen only in singly bound form
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/14—Preparation of carboxylic acid esters from carboxylic acid halides
-
- 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
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
- C07C2601/08—Systems containing only non-condensed rings with a five-membered ring the ring being saturated
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/18—Systems containing only non-condensed rings with a ring being at least seven-membered
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/36—Systems containing two condensed rings the rings having more than two atoms in common
- C07C2602/42—Systems containing two condensed rings the rings having more than two atoms in common the bicyclo ring system containing seven carbon atoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Materials For Photolithography (AREA)
Abstract
The invention discloses a photoresist acid-sensitive resin monomer with good alkali solubility, a synthesis method and application thereof, and relates toThe field of photoresist resin monomers, the structural formula of the photoresist resin monomer is as follows:
wherein R is1Is methyl or hydrogen, R2Is an alkyl group, and is,
is an alicyclic ring of 3-15 carbon atoms, R3Is an alkyl group. The resin monomer can increase the etching resistance of the photoresist, improve the adhesion with a wafer, increase the alkali solubility difference of the photoresist before and after exposure, and is beneficial to improving the line edge roughness of the photoresist and improving the resolution.
Description
Technical Field
The invention relates to the field of photoresist resin monomers, in particular to a photosensitive resin monomer and a synthesis 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 are resin, photoacid generator, and corresponding additives and solvents, and these materials have chemical sensitivity with light (including visible light, ultraviolet light, electron beam, etc.) and undergo a photochemical reaction to change their solubility in a developing solution. 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 photoetching developer of the positive photoresist is alkaline, tetramethylammonium hydroxide (TMAH) is commonly used, the dissolution speed difference is required to exist in the developer before and after the photoresist is exposed, the resolution and the edge roughness of a photoetching pattern are greatly influenced by the difference, the dissolution difference depends on the property difference before and after the photosensitive resin monomer is exposed, and some polymerized units containing lactone structures also have the function of improving the dissolution difference. Common photosensitive monomers include: cyclic tert-butyl alcohol ester structure, hemiacetal (ketone) structure, tert-butyl alcohol ester structure.
Disclosure of Invention
The invention provides a photoresist acid-sensitive resin monomer with good alkali solubility, and a synthesis method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a photoresist acid-sensitive resin monomer with good alkali solubility, wherein the structural formula of the photoresist acid-sensitive resin monomer is as follows:
wherein R is1Is methyl or hydrogen, R2Is an alkyl group, and is,
is an alicyclic ring of 3-15 carbon atoms, R3Is an alkyl group.
Preferably, the photoresist acid-sensitive resin monomer is specifically selected from one of the following structures:
the synthesis method of the photoresist acid-sensitive resin monomer with good alkali solubility comprises the following synthesis routes:
the synthesis steps are as follows:
s1: the method comprises the following steps of (1) taking cyclic ketone I containing carbon-carbon double bonds as an initial raw material, carrying out addition reaction on the cyclic ketone I and a halogen simple substance in a first reaction solvent to generate two halogen substituted intermediates II, wherein the first reaction solvent is selected from one or more of dichloromethane, chloroform and toluene;
s2: the intermediate II reacts with an alcohol raw material R under the action of strong alkali3OH reacts in a second reaction solvent to form an intermediate III with an ether structure; the second reaction solvent is selected from one or more of N, N-dimethylformamide, dimethyl sulfoxide and tetrahydrofuran;
s3: the intermediates III and R2Carrying out a Grignard reaction on the MgX format reagent in a third reaction solvent to generate an intermediate IV with a tertiary alcohol structure; the third reaction solvent is selected from anhydrous diethyl ether or anhydrous tetrahydrofuran;
s4: the intermediate IV and (methyl) acrylic acid or (methyl) acryloyl chloride are subjected to esterification reaction in a fourth reaction solvent to generate a photoresist acid-sensitive resin monomer V; the fourth reaction solvent is one or more of dichloromethane, chloroform and toluene.
Preferably, in S1, the cyclic ketone i is selected from one of the following structures:
preferably, in S2, at least one of the following technical features is further included:
a1) the strong base is selected from sodium hydride, sodium hydroxide, potassium hydroxide, sodium tert-butoxide or potassium tert-butoxide;
a2) the alcohol raw material R3OH is selected from methanol, ethanol, n-propanol, isopropanol and tert-butanol.
Preferably, in S3, R is2Mg is selected from one of the following structures:
preferably, another synthetic route of the intermediate III is as follows:
a1: the initial raw material is cyclic ketone I containing carbon-carbon double bond double bonds, and the cyclic ketone I and an oxidant are subjected to oxidation reaction to generate an intermediate VI with an epoxy structure;
a2: hydrolyzing the intermediate VI to obtain a diol intermediate VII under an acidic condition;
a3: and removing HX from the intermediate VII and R3X under basic conditions to generate an intermediate III.
Preferably, at least one of the following technical characteristics is also included:
a1, wherein the oxidant is selected from m-chloroperoxybenzoic acid or hydrogen peroxide;
in A2, the acid is selected from hydrochloric acid or sulfuric acid;
a3, wherein the base is selected from one of sodium hydride, sodium hydroxide, potassium hydroxide, sodium tert-butoxide and potassium tert-butoxide.
The photoresist acid-sensitive resin monomer with good alkali solubility is used for preparing photoresist.
Compared with the prior art, the invention has the following beneficial effects: the invention provides a photoresist acid-sensitive resin monomer with good alkali solubility, which comprises an alicyclic ring, wherein two ethers are connected on adjacent carbon atoms on the alicyclic ring, and the carbon atoms connected with acrylate or methacrylate on the ring are in a tertiary carbon structure.
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.
Example 1
Dissolving 2-cyclopentene-1-one I-a (20g, 244mmol) in dichloromethane (300mL), cooling to 0 ℃ in ice water bath, slowly adding liquid bromine (42.8g, 268mmol) under nitrogen protection, heating the reaction solution to room temperature, stirring for 2 hours, quenching the reaction solution with saturated sodium thiosulfate (50mL), adding water (100mL), separating, extracting the aqueous phase with dichloromethane (100mL x 3) for three times, combining the organic phases, washing the combined organic phases with saturated saline (100mL), drying with anhydrous sodium sulfate, and drying the organic phase under vacuum to obtain intermediate II-a (57.2g, 236mmol, yield: 97.1%).
Sodium hydride (23g, 958mmol) was added to N, N-dimethylformamide (200mL), cooled to 0 deg.C, methanol (30g, 936mmol) was slowly added dropwise, warmed to 80 deg.C and stirred for half an hour, cooled to 0 deg.C, N-dimethylformamide (200mL) of intermediate II-a (57.2g, 236mmol) was slowly added dropwise, after completion of the addition, warmed to 80 deg.C and stirred for 5 hours, the reaction was cooled to room temperature, poured slowly into ice water (200mL), extracted three times with ethyl acetate (300 mL. about.3), the combined organic phases were washed with saturated brine (300mL), dried over anhydrous sodium sulfate, and the organic phases were dried under vacuum to give intermediate III-a (31.7g, 220mmol, 93.0%).
Adding magnesium (8g, 329mmol) into anhydrous ether (100mL), adding small-particle iodine, under the protection of nitrogen, slowly adding a solution of methyl bromide (5g, 53mmol) in ether (20mL) slowly, heating to keep the solution slightly boiling, removing iodine color, continuously adding a solution of methyl bromide (26.3g, 277mmol) in ether (100mL), refluxing for half an hour, cooling to 0 ℃, adding a solution of III-a (31.7g, 220mmol) in ether (200mL), stirring at room temperature for reaction for 2 hours, cooling with ice water, adding 20% dilute sulfuric acid to quench the reaction, separating, extracting the aqueous phase with ethyl acetate (200mL x 3) for three times, washing the organic phase with saturated saline, drying with anhydrous sodium sulfate, and drying under vacuum to obtain intermediate IV-a (29.6g, 185mmol, yield: 84.0%).
Adding the intermediate IV-a (29.6g, 185mmol) into dichloromethane (300mL), adding triethylamine (47g, 464mmol), cooling to 0 ℃, adding acryloyl chloride (20.1g, 222mmol) dropwise, heating to room temperature, stirring for 4 hours, adding water (200mL), quenching the reaction, extracting the aqueous phase with dichloromethane (200mL x 3) three times, combining the organic phases, washing with saturated saline (200mL), drying with anhydrous sodium sulfate, and spin-drying under vacuum to obtain a crude product, which is purified by distillation to obtain the resin monomer V-a (37.5g, 175mmol, yield: 94.7%). Another synthesis of intermediate III-a is provided:
2-cyclopenten-1-one I-a (20g, 244mmol) was added to methanol (200mL), sodium hydroxide (29.2g, 730mmol) was added, a 30% hydrogen peroxide solution (83g) was slowly dropped, stirred at room temperature for 1 hour, filtered, the filtrate was quenched with a saturated solution of sodium thiosulfate, concentrated under vacuum to remove most of the methanol, supplemented with water (150mL), the aqueous phase was extracted three times with ethyl acetate (200 mL. times.3), the organic phases were combined, washed with saturated brine (150mL), dried over anhydrous sodium sulfate, and spin-dried under vacuum to give intermediate VI-a (21.5g, 219mmol, yield: 90%).
Intermediate VI-a (21.5g, 219mmol) was added to 20% dilute aqueous sulfuric acid (200mL) and stirred for 1 hour, the pH was adjusted to neutral with sodium carbonate, dried under vacuum, methanol (150mL) was added and stirred, the solid was removed by filtration and the organic phase dried under vacuum to give intermediate VII-a (23.7g, 204mmol, yield: 93.1%).
Adding sodium hydride (12.3g, 513mmol) into anhydrous N, N-dimethylformamide (300mL) under the cooling of an ice-water bath, slowly dropwise adding intermediate VII-a (23.7g, 204mmol), raising the temperature to room temperature, stirring for half an hour, cooling the mixture in the ice-water bath to below 10 ℃, slowly dropwise adding methyl iodide (63.7g, 449mmol), raising the temperature to room temperature after dropwise adding, continuing stirring for 3 hours, cooling ice water to below 10 ℃, quenching the reaction by using a 10% sodium hydroxide aqueous solution, extracting the aqueous phase by using ethyl acetate (200mL, 3) for three times, combining organic phases, washing the organic phases by using saturated common salt water, drying the organic phases by using anhydrous sodium sulfate, and performing rotary drying under vacuum to obtain intermediate III-a (27.6g, 191mmol, yield: 93.8%).
Example 2
Bicyclo [2.2.1] hept-5-en-2-one I-b (20g, 185mmol) was dissolved in dichloromethane (300mL), cooled to 0 ℃ in an ice water bath, bromine (29.6g, 185mmol) was slowly added dropwise under nitrogen, the reaction solution was allowed to warm to room temperature, stirred and reacted for 2 hours, the reaction solution was quenched with saturated sodium thiosulfate (50mL), water (100mL) was added for dilution, liquid separation was performed, the aqueous phase was extracted three times with dichloromethane (100 mL. times.3), the organic phases were combined, the combined organic phases were washed with saturated brine (100mL), dried over anhydrous sodium sulfate, and the organic phase was dried under vacuum to give intermediate II-b (47.3g, 177mmol, yield: 95.4%).
Sodium hydride (17g, 708mmol) was added to N, N-dimethylformamide (200mL), cooled to 0 deg.C, methanol (22.7g, 708mmol) was slowly added dropwise, warmed to 80 deg.C and stirred for half an hour, cooled to 0 deg.C, N-dimethylformamide (200mL) of intermediate II-b (47.3g, 177mmol) was slowly added dropwise, after completion of the dropwise addition, warmed to 80 deg.C and stirred for 5 hours, the reaction was cooled to room temperature, slowly poured into ice water (200mL), extracted with ethyl acetate (300 mL. multidot.3) three times, the combined organic phases were washed with saturated brine (300mL), dried over anhydrous sodium sulfate, and the organic phase was dried under vacuum to give intermediate III-b (27.5g, 162mmol, yield: 91.5%).
Adding magnesium (6g, 247mmol) into anhydrous ether (100mL), adding small-particle iodine, slowly adding a solution of methyl bromide (5g, 53mmol) in diethyl ether (20mL) under the protection of nitrogen, heating to keep the solution slightly boiling, continuously adding a solution of methyl bromide (18g, 190mmol) in diethyl ether (100mL), refluxing for half an hour, cooling to 0 ℃, adding a solution of intermediate III-b (27.5g, 137mmol) in diethyl ether (200mL), stirring at room temperature for reaction for 2 hours, cooling with ice water, adding 20% dilute sulfuric acid to quench the reaction, separating, extracting the aqueous phase with ethyl acetate (200mL 3) for three times, washing the organic phase with saturated saline, drying with anhydrous sodium sulfate, and performing rotary drying under vacuum to obtain intermediate IV-b (27.5g, 137mmol, yield: 85.0%).
Intermediate IV-b (27.5g, 137mmol) was added to dichloromethane (300mL), triethylamine (35g, 346mmol) was added, cooled to 0 deg.C, acryloyl chloride (15g, 166mmol) was added dropwise, allowed to warm to room temperature and stirred for 4 hours, the reaction was quenched with water (200mL), the aqueous phase was extracted three times with dichloromethane (200mL x 3), the combined organic phases were washed with saturated brine (200mL), dried over anhydrous sodium sulfate, and dried under vacuum to give crude product, which was purified by distillation to give resin monomer V-b (32.6g, 128mmol, yield: 93.4%).
Example 3
4, 4-dimethyl-2-cyclohexyl-1-keto I-c (20g, 161mmol) was dissolved in dichloromethane (300mL), cooled to 0 ℃ in an ice water bath, bromine (28.3g, 177mmol) was slowly added dropwise under nitrogen, the reaction was allowed to warm to room temperature, stirred for 2 hours, quenched with saturated sodium thiosulfate (50mL), diluted with water (100mL), separated, the aqueous phase extracted three times with dichloromethane (100 mL. times.3), the organic phases combined, the combined organic phases washed with saturated brine (100mL), dried over anhydrous sodium sulfate, and the organic phase was dried under vacuum to give intermediate II-c (44.2g, 156mmol, yield: 96.6%).
Sodium hydride (15g, 625mmol) was added to N, N-dimethylformamide (200mL), cooled to 0 deg.C, methanol (20g, 624mmol) was slowly added dropwise, warmed to 80 deg.C and stirred for half an hour, cooled to 0 deg.C, N-dimethylformamide (200mL) of intermediate II-c (44.2g, 156mmol) was slowly added dropwise, after completion of the addition, warmed to 80 deg.C and stirred for 5 hours, the reaction was cooled to room temperature, poured slowly into ice water (200mL), extracted three times with ethyl acetate (300 mL. multidot.3), the combined organic phases were washed with saturated brine (300mL), dried over anhydrous sodium sulfate, and the organic phases were dried under vacuum to give intermediate III-c (27.4g, 147mmol, yield: 94.5%).
Adding magnesium (5.4g, 222mmol) into anhydrous ether (100mL), adding small-particle iodine, under the protection of nitrogen, slowly adding a solution of methyl bromide (5g, 53mmol) in ether (20mL), heating to keep the solution slightly boiling, removing iodine color, continuously adding a solution of methyl bromide (11.8g, 124mmol) in ether (100mL), refluxing for half an hour, cooling to 0 ℃, adding a solution of intermediate III-c (27.4g, 147mmol) in ether (200mL), stirring at room temperature for 2 hours, cooling with ice water, adding 20% dilute sulfuric acid to quench the reaction, separating, extracting the aqueous phase with ethyl acetate (200mL 3) for three times, washing the organic phase with saturated saline, drying with anhydrous sodium sulfate, and drying under vacuum to obtain intermediate IV-c (28.2g, 139mmol, yield: 94.8%).
Adding the intermediate IV-c (28.2g, 139mmol) into dichloromethane (300mL), adding triethylamine (42.3g, 418mmol), cooling to 0 ℃, dropwise adding acryloyl chloride (14g, 155mmol), heating to room temperature, stirring for 4 hours, adding water (200mL), quenching the reaction, extracting the aqueous phase with dichloromethane (200mL x 3) for three times, combining the organic phases, washing with saturated saline (200mL), drying with anhydrous sodium sulfate, and spin-drying under vacuum to obtain a crude product, which is purified by distillation to obtain the resin monomer V-c (34.5g, 135mmol, yield: 96.5%).
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (9)
1. The photoresist acid-sensitive resin monomer with good alkali solubility is characterized in that the structural formula of the photoresist acid-sensitive resin monomer is as follows:
wherein R is1Is methyl or hydrogen, R2Is an alkyl group, and is,
is an alicyclic ring of 3-15 carbon atoms, R3Is an alkyl group.
2. The photoresist acid-sensitive resin monomer with good alkali solubility of claim 1, wherein the photoresist acid-sensitive resin monomer is specifically selected from one of the following structures:
3. the method for synthesizing the acid-sensitive resin monomer for photoresist with good alkali solubility according to claim 1 or 2, which is characterized by comprising the following synthetic route:
the synthesis steps are as follows:
s1: the method comprises the following steps of (1) taking cyclic ketone I containing carbon-carbon double bonds as an initial raw material, carrying out addition reaction on the cyclic ketone I and a halogen simple substance in a first reaction solvent to generate two halogen substituted intermediates II, wherein the first reaction solvent is one or more of dichloromethane, chloroform and toluene;
s2: the intermediate II reacts with an alcohol raw material R under the action of strong alkali3OH reacts in a second reaction solvent to form an intermediate III with an ether structure; the second reaction solvent is N, N-dimethylformamideOne or more of dimethyl sulfoxide and tetrahydrofuran;
s3: the intermediates III and R2Carrying out a Grignard reaction on the MgX format reagent in a third reaction solvent to generate an intermediate IV with a tertiary alcohol structure; the third reaction solvent is anhydrous diethyl ether or anhydrous tetrahydrofuran;
s4: the intermediate IV and (methyl) acrylic acid or (methyl) acryloyl chloride are subjected to esterification reaction in a fourth reaction solvent to generate a photoresist acid-sensitive resin monomer V; the fourth reaction solvent is one or more of dichloromethane, chloroform and toluene.
4. The acid-sensitive resin monomer for resists with good alkali solubility of claim 3, wherein in S1, the cyclic ketone I is selected from one of the following structures:
5. the acid-sensitive resin monomer for photoresist with good alkali solubility according to claim 3, wherein S2 further comprises at least one of the following technical features:
a1) the strong base is selected from sodium hydride, sodium hydroxide, potassium hydroxide, sodium tert-butoxide or potassium tert-butoxide;
a2) the alcohol raw material R3OH is selected from methanol, ethanol, n-propanol, isopropanol or tert-butanol.
6. The acid-sensitive resin monomer for photoresist with good alkali solubility of claim 3, wherein R in S3 is2MgX is selected from one of the following structures:
7. the method for synthesizing the photoresist acid-sensitive resin monomer with good alkali solubility according to claim 3, wherein the other synthetic route of the intermediate III is as follows:
the synthesis steps are as follows:
a1: the initial raw material is cyclic ketone I containing carbon-carbon double bond double bonds, and the cyclic ketone I and an oxidant are subjected to oxidation reaction to generate an intermediate VI with an epoxy structure;
a2: hydrolyzing the intermediate VI to obtain a diol intermediate VII under an acidic condition;
a3: the intermediate VII and R3And removing HX from X under alkaline conditions to generate an intermediate III.
8. The method for synthesizing acid-sensitive resin monomer for photoresist with good alkali solubility according to claim 7, further comprising at least one of the following technical features:
in A1, the oxidizing agent is m-chloroperoxybenzoic acid or hydrogen peroxide;
in A2, the acid is selected from hydrochloric acid or sulfuric acid;
a3, wherein the base is selected from one of sodium hydride, sodium hydroxide, potassium hydroxide, sodium tert-butoxide and potassium tert-butoxide.
9. The photoresist acid-sensitive resin monomer with good alkali solubility according to claim 1 or 2 is used for preparing photoresist.
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| CN114213246A (en) * | 2021-12-29 | 2022-03-22 | 徐州博康信息化学品有限公司 | Preparation method of photoresist resin monomer |
| CN114380688A (en) * | 2021-12-28 | 2022-04-22 | 徐州博康信息化学品有限公司 | Preparation method of acid-sensitive photoresist resin monomer |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004042477A1 (en) * | 2002-11-04 | 2004-05-21 | Dongjin Semichem Co., Ltd. | Chemically amplified polymer having pendant group with dicyclohexyl and resist composition comprising the same |
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2021
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004042477A1 (en) * | 2002-11-04 | 2004-05-21 | Dongjin Semichem Co., Ltd. | Chemically amplified polymer having pendant group with dicyclohexyl and resist composition comprising the same |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114380688A (en) * | 2021-12-28 | 2022-04-22 | 徐州博康信息化学品有限公司 | Preparation method of acid-sensitive photoresist resin monomer |
| CN114380688B (en) * | 2021-12-28 | 2023-12-29 | 徐州博康信息化学品有限公司 | Preparation method of acid-sensitive photoresist resin monomer |
| CN114213246A (en) * | 2021-12-29 | 2022-03-22 | 徐州博康信息化学品有限公司 | Preparation method of photoresist resin monomer |
| CN114213246B (en) * | 2021-12-29 | 2023-11-14 | 徐州博康信息化学品有限公司 | Preparation method of photoresist resin monomer |
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