CN112925166A - High-resolution photoresist - Google Patents
High-resolution photoresist Download PDFInfo
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- CN112925166A CN112925166A CN202110089845.2A CN202110089845A CN112925166A CN 112925166 A CN112925166 A CN 112925166A CN 202110089845 A CN202110089845 A CN 202110089845A CN 112925166 A CN112925166 A CN 112925166A
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- Prior art keywords
- ester
- photoresist
- high resolution
- photoacid generator
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- 229920002120 photoresistant polymer Polymers 0.000 title claims abstract description 64
- 239000002253 acid Substances 0.000 claims abstract description 32
- 238000009792 diffusion process Methods 0.000 claims abstract description 23
- 239000003112 inhibitor Substances 0.000 claims abstract description 23
- 239000011347 resin Substances 0.000 claims abstract description 18
- 229920005989 resin Polymers 0.000 claims abstract description 18
- 150000005690 diesters Chemical group 0.000 claims abstract description 16
- 239000003960 organic solvent Substances 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 3
- -1 sulfonium salt cation Chemical class 0.000 claims description 38
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 11
- 239000000178 monomer Substances 0.000 claims description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 150000002596 lactones Chemical class 0.000 claims description 6
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical group [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 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 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 238000005886 esterification reaction Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 claims description 4
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 4
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 4
- TUVYSBJZBYRDHP-UHFFFAOYSA-N acetic acid;methoxymethane Chemical compound COC.CC(O)=O TUVYSBJZBYRDHP-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 4
- 150000002148 esters Chemical group 0.000 claims description 4
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical class O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 3
- 235000010265 sodium sulphite Nutrition 0.000 claims description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 2
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 claims description 2
- QLNYTCSELYEEPV-UHFFFAOYSA-N 2,2-dimethylpropyl acetate Chemical compound CC(=O)OCC(C)(C)C QLNYTCSELYEEPV-UHFFFAOYSA-N 0.000 claims description 2
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 claims description 2
- PPPFYBPQAPISCT-UHFFFAOYSA-N 2-hydroxypropyl acetate Chemical compound CC(O)COC(C)=O PPPFYBPQAPISCT-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 2
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical group C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 claims description 2
- 229930188620 butyrolactone Natural products 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 238000013329 compounding Methods 0.000 claims description 2
- GCFAUZGWPDYAJN-UHFFFAOYSA-N cyclohexyl 3-phenylprop-2-enoate Chemical compound C=1C=CC=CC=1C=CC(=O)OC1CCCCC1 GCFAUZGWPDYAJN-UHFFFAOYSA-N 0.000 claims description 2
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 claims description 2
- 229940116333 ethyl lactate Drugs 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 claims description 2
- OUUQCZGPVNCOIJ-UHFFFAOYSA-N hydroperoxyl Chemical group O[O] OUUQCZGPVNCOIJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000003367 polycyclic group Chemical group 0.000 claims description 2
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 claims description 2
- 235000019252 potassium sulphite Nutrition 0.000 claims description 2
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000001259 photo etching Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 239000004677 Nylon Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 230000010355 oscillation Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- ZFEAYIKULRXTAR-UHFFFAOYSA-M triphenylsulfanium;chloride Chemical compound [Cl-].C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 ZFEAYIKULRXTAR-UHFFFAOYSA-M 0.000 description 1
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Classifications
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
-
- 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
- C07C309/17—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing carboxyl groups bound to the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C381/00—Compounds containing carbon and sulfur and having functional groups not covered by groups C07C301/00 - C07C337/00
- C07C381/12—Sulfonium compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/281—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Materials For Photolithography (AREA)
Abstract
The embodiment of the invention provides a high-resolution photoresist, which comprises the following raw materials: 0.1 to 10 parts by weight of a photoacid generator, 10 to 30 parts by weight of a film-forming resin, 0.1 to 5 parts by weight of an acid diffusion inhibitor, and 55 to 89.8 parts by weight of an organic solvent A; wherein the photoacid generator is a photoacid generator containing a diester structure, the acid diffusion inhibitor is an acid diffusion inhibitor with an ester bond, and the molecular weight of the acid diffusion inhibitor with an ester bond is 100-30000 g/mol. According to the photoresist provided by the embodiment of the invention, under the condition of adopting the photoacid generator containing the diester structure, the line width roughness of the photoresist is further improved, the resolution of the photoresist is improved, and the film forming capability of the photoresist is enhanced by adding the acid diffusion inhibitor with ester bonds.
Description
Technical Field
The invention relates to the technical field of photoresist, in particular to high-resolution photoresist.
Background
The photoresist (also called as photoresist) refers to a resist film material whose solubility changes by irradiation or radiation of light sources such as ultraviolet light, excimer laser, electron beam, ion beam, and X-ray. The method is mainly used for the micro-processing of integrated circuits and semiconductor discrete devices, and also has wide application in the manufacturing processes of flat panel displays, LEDs, flip chip packages, magnetic heads, precision sensors and the like. Because the photoresist has photochemical sensitivity, the photoresist can be used for carrying out photochemical reaction to coat the photoresist on a semiconductor, a conductor and an insulator, the part left after exposure and development has the protective effect on the bottom layer, and then the required micro-pattern can be transferred from a mask to a substrate to be processed by etching with an etchant. In addition to the main resin and the photoacid generator, an acid diffusion inhibitor is often added to the photoresist, which mainly has the main function of preventing the dissolution of the film-forming resin before exposure to play a role in dissolution inhibition, and the acid generated by the photoacid generator in the photoresist after exposure catalyzes the dissolution to remove acid-sensitive groups, so that the acid diffusion inhibitor is changed into a polar compound to further promote the dissolution of the resin, thereby increasing the dissolution contrast of the non-exposed area and the exposed area and improving the resolution of the resist. At present, the acid diffusion inhibitor available in the market for photoresist only adds a certain amount of hydroxyl groups in the structure to enhance the compatibility between the structure and the resin, and the technical solution of how to further improve the resolution of the photoresist is not solved. Therefore, the prior art still needs to be improved.
Disclosure of Invention
The embodiment of the invention provides a high-resolution photoresist, wherein a photoacid generator which is beneficial to generating effective controllable large-volume acid and contains a diester structure is adopted in the photoresist to improve the line width and the roughness of a circuit manufactured by using the photoresist, and meanwhile, an acid diffusion inhibitor with an ester bond is adopted in the photoresist to further improve the resolution of the photoresist.
The embodiment of the invention provides a high-resolution photoresist which comprises the following raw materials: 0.1 to 10 parts by weight of a photoacid generator, 10 to 30 parts by weight of a film-forming resin, 0.1 to 5 parts by weight of an acid diffusion inhibitor having an ester bond, and 55 to 89.8 parts by weight of an organic solvent A;
the photoacid generator is a photoacid generator containing a diester structure, and the specific structural general formula is as follows:
wherein R is1、R2One or more of an alkyl group having 1 to 40 hydrogen atoms and 1 to 20 carbon atoms, an aryl group, and a substituent containing a sulfur/oxygen heteroatom, wherein Q + is a sulfonium salt cation or an iodonium salt cation;
the acid diffusion inhibitor is an acid diffusion inhibitor with ester bonds, the molecular weight of the acid diffusion inhibitor is 100-30000g/mol, and the specific structural formula is as follows:
wherein R is3、R4Is one or more of an alkyl group having 1 to 40 hydrogen atoms and 1 to 20 carbon atoms, an aryl group, or a substituent containing a sulfur/oxygen/nitrogen heteroatom, and na is a carbon chain having 1 to 20 carbon atoms and containing an ester bond.
Preferably, in the high resolution photoresist, the method for preparing the photoacid generator containing a diester structure comprises:
s1, dissolving maleic anhydride in the organic solvent B, adding an alcohol organic compound and a catalyst, uniformly stirring, and heating to perform an esterification reaction to obtain a succinate compound;
s2, uniformly mixing the succinate compound and sulfite in an aqueous solution, and heating for reaction to obtain diester sulfonate;
s3, compounding the diester sulfonate and an aqueous solution containing sulfonium salt cations or iodonium salt cations to generate the photoacid generator containing the diester structure.
More preferably, in the high resolution photoresist, the organic solvent B is one or more of toluene, dichloroethane or 4-dimethylaminopyridine.
More preferably, in the high resolution photoresist, the catalyst is one or more of concentrated sulfuric acid and p-toluenesulfonic acid.
More preferably, in the high resolution photoresist, the alcohol organic compound is a saturated alcohol organic compound.
More preferably, in the high resolution photoresist, the temperature of the esterification reaction in S1 is 50-110 ℃ and the temperature of the reaction in S2 is 50-110 ℃.
More preferably, in the high resolution photoresist, the sulfite is sodium sulfite or potassium sulfite.
Preferably, in the high resolution photoresist, the film-forming resin is prepared from at least one acid-reactive monomer, and the specific structural formula of the acid-reactive monomer is as follows:
wherein R isaH or a carbon chain with 1-20 carbon atoms; rbIs an acid-sensitive quaternary carbon, RcH or a carbon chain with 1-20 carbon atoms; rdIs polar group-containing (meth) acrylate.
More preferably, in the high resolution photoresist, R isbThe catalyst is a quaternary ester with 6-30 carbon atoms, all hydrogen atoms of carbon atoms connected with hydroxyl oxygen atoms are substituted by other groups, and the structure of the quaternary ester is one or more of tert-butyl ester, substituted tert-butyl ester, alkyl-substituted adamantane derivative ester, alkyl-substituted norbornyl derivative ester, alkyl-substituted cyclic alkyl ester and alkyl-substituted cyclic alkyl derivative ester;
the R isdThe structure of the compound is one or more of adamantyl ester containing 1 or more independent hydroxyl groups, cyclohexyl ester containing 1 or more independent hydroxyl groups, cyclopentyl ester containing 1 or more independent hydroxyl groups, polycycloester compound containing 1 or more independent hydroxyl groups, caged ester compound containing 1 or more independent hydroxyl groups, butyrolactone, valerolactone, substituted valerolactone, caprolactone, substituted caprolactone, lactone containing a adamantane structure, lactone containing a polycyclic structure and lactone containing a caged structure.
Preferably, in the high resolution photoresist, the organic solvent a is one or more of methyl ether acetate, propylene glycol monoacetate, propylene glycol monoethyl ether, propylene glycol methyl ether acetate, diethylene glycol methyl ether, diethylene glycol diethyl ether, butyl acetate, neopentyl acetate, ethyl lactate, methyl ethyl ketone, cyclohexanone and methyl isobutyl ketone.
According to the high-resolution photoresist disclosed by the embodiment of the invention, the line width and the roughness of a circuit manufactured by utilizing the photoresist are improved by adopting the photoacid generator containing the diester structure, which is beneficial to generating effective controllable large-volume acid, in the photoresist, and meanwhile, the distribution of the photoacid generator in the photoresist can be more effectively improved by adopting the acid diffusion inhibitor with ester bonds in the photoresist, so that the resolution and the line width roughness of the photoresist are further improved, and the film forming capability of the photoresist is improved.
Drawings
FIG. 1 is a photo-lithographic image obtained by photo-lithography of the photoresist prepared in example 1 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to specific embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. 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.
The high-resolution photoresist provided by the embodiment of the invention adopts a photoacid generator containing a diester structure, an acid diffusion inhibitor with an ester bond and a film-forming resin with a specific structure, and the photoacid generator, the acid diffusion inhibitor and the film-forming resin are mixed together to show better photoetching performance. In the exposure process of the photoresist, the photoacid generator containing the diester structure can generate effective and controllable large-volume acid, and the photoacid is controlled to react in an exposure area under the assistance of an acid diffusion inhibitor, so that the roughness of a pattern is improved, and the resolution of the photoresist is improved. Meanwhile, the photoresist has stronger polarity, is compatible with film-forming resin, improves the film-forming property, and effectively avoids the problems of brittle fracture, peeling and the like of the photoresist film on the premise of ensuring the stable photoetching property of the photoresist.
Example 1
A preparation method of a high-resolution photoresist comprises the following steps:
0.25g of photoacid generator containing diester structure, 8.5g of film-forming resin, 0.06g of acid diffusion inhibitor and 80g of organic solvent A are uniformly mixed in a 100mL glass bottle and subjected to light-proof oscillation for 24 hours, after the oscillation is finished, the mixed solution is filtered by a 0.22 micron filter, then the mixed solution is filtered by a 0.02 micron filter, and the collected filtrate is the high-resolution photoresist solution.
Specifically, the preparation method of the photoacid generator containing the diester structure comprises the following steps:
s1, dissolving 98g of maleic anhydride in 100g of toluene under the protection of nitrogen, adding 220g of cyclohexanol and 50g of p-toluenesulfonic acid, uniformly stirring, heating to 90 ℃ to perform esterification reaction for 12 hours, adding 100g of ethyl acetate, washing twice by using 50mL of deionized water, drying an organic layer, desolventizing to obtain 162g of succinate compound, and measuring the conversion rate to be 58%, wherein the reaction equation is as follows:
s2, dissolving 56g of succinate compound in 200g of deionized water, adding 25g of sodium sulfite, uniformly mixing, reacting at 100 ℃ for 24 hours, extracting with 500g of ethyl acetate after the reaction is finished, and then desolventizing to obtain 47g of diester sodium sulfonate compound, wherein the conversion rate is 61%, and the reaction equation is as follows:
s3, dissolving 38g of diester sodium sulfonate compound in 100g of deionized water, dropwise adding 150g of triphenyl sulfonium chloride salt aqueous solution (mass fraction is 20%), stirring for 12 hours, extracting with 500g of dichloromethane, washing twice with 50g of deionized water, drying with anhydrous magnesium sulfate after washing, desolventizing to obtain 38g of photoacid generator containing a diester structure, and measuring the conversion rate to be 62%, wherein the reaction equation is as follows:
wherein the molecular weight of the acid diffusion inhibitor with ester bond is 6500, the molecular weight distribution is 2.21, and the structural formula is as follows:
the preparation method of the film-forming resin comprises the following steps: adding 45g of monomer 1, 50g of monomer 2 and 20g of monomer 3 into a reaction kettle filled with nitrogen, adding 60g of ethyl acetate into the reaction kettle, uniformly stirring to obtain a monomer mixed solution, heating the reaction kettle to 77 ℃, mixing 10g of ethyl acetate with 12g of benzoyl peroxide to obtain an initiator mixed solution, dropwise adding the initiator mixed solution into the reaction kettle of the monomer mixed solution, reacting at 77 ℃ for 7 hours, stopping the reaction, cooling the reaction kettle to room temperature, adding 600g of methanol into the reaction kettle cooled to room temperature, discharging the liquid in the reaction kettle after 1 hour of a first precipitate is generated, and adding 70g of ethyl acetate into the reaction kettle until the first precipitate is dissolved. Adding 600g of methanol into the reaction kettle to generate a second precipitate, discharging the liquid in the reaction kettle to obtain the second precipitate, placing the second precipitate in vacuum for drying to obtain 76g of methacrylate resin, and measuring the conversion rate to be 66%, wherein the structural formula of the film-forming resin is as follows:
in addition, the structural formulas of the monomer 1, the monomer 2 and the monomer 3 are as follows in sequence:
the organic solvent A is formed by mixing methyl ether acetate and propylene glycol monoethyl ether, the mass ratio of the methyl ether acetate to the propylene glycol monoethyl ether is 2:3, the filter is made of nylon or UPE, and in the embodiment, the nylon filter is preferred.
The high-resolution photoresist prepared by the method is rotated on a No. 12 silicon wafer at the speed of 2500 rpm to form a film, then the film is baked for 90s on a hot plate at the temperature of 120 ℃, and the film is baked on an exposure machine at the exposure intensity of 45mJ/cm2The exposure is carried out by illumination, the substrate is baked for 90s on a hot plate at 110 ℃ after the exposure is finished, finally the substrate is developed for 60s in 2.38% TMAH developing solution, then the substrate is dried and is detected by an electron microscope for photoetching, and the obtained photoetching image is shown in figure 11, the photoresist prepared by the embodiment of the invention reduces the line width and the line width roughness of a manufactured circuit, wherein the photoacid generator containing a diester structure can generate effective controllable large-volume acid, and meanwhile, the high-resolution photoresist can be prepared after the photoacid generator with an ester bond is added, so that the resolution of the photoresist is greatly improved; meanwhile, the coating is compatible with resin, so that the adhesiveness after film formation is improved, and the overall performance of the photoresist is improved.
While the invention has been described with reference to specific embodiments, the invention is not limited thereto, and various equivalent modifications and substitutions can be easily made by those skilled in the art within the technical scope of the invention.
Claims (10)
1. A high resolution photoresist, comprising the following raw materials: 0.1 to 10 parts by weight of a photoacid generator, 10 to 30 parts by weight of a film-forming resin, 0.1 to 5 parts by weight of an acid diffusion inhibitor having an ester bond, and 55 to 89.8 parts by weight of an organic solvent A;
the photoacid generator is a photoacid generator containing a diester structure, and the specific structural general formula is as follows:
wherein R is1、R2One or more of an alkyl group having 1 to 40 hydrogen atoms and 1 to 20 carbon atoms, an aryl group, and a substituent containing a sulfur/oxygen heteroatom, wherein Q + is a sulfonium salt cation or an iodonium salt cation;
the acid diffusion inhibitor is an acid diffusion inhibitor with ester bonds, the molecular weight of the acid diffusion inhibitor is 100-30000g/mol, and the specific structural formula is as follows:
wherein R is3、R4Is one or more of an alkyl group having 1 to 40 hydrogen atoms and 1 to 20 carbon atoms, an aryl group, or a substituent containing a sulfur/oxygen/nitrogen heteroatom, and na is a carbon chain having 1 to 20 carbon atoms and containing an ester bond.
2. The high resolution photoresist according to claim 1, wherein the photoacid generator having a diester structure is prepared by:
s1, dissolving maleic anhydride in the organic solvent B, adding an alcohol organic compound and a catalyst, uniformly stirring, and heating to perform an esterification reaction to obtain a succinate compound;
s2, uniformly mixing the succinate compound and sulfite in an aqueous solution, and heating for reaction to obtain diester sulfonate;
s3, compounding the diester sulfonate and an aqueous solution containing sulfonium salt cations or iodonium salt cations to generate the photoacid generator containing the diester structure.
3. The high resolution photoresist according to claim 2, wherein the organic solvent B is one or more of toluene, dichloroethane, or 4-dimethylaminopyridine.
4. The high resolution photoresist of claim 2, wherein the catalyst is one or more of concentrated sulfuric acid and p-toluenesulfonic acid.
5. The high resolution photoresist according to claim 2, wherein the alcohol organic compound is a saturated alcohol organic compound.
6. The high resolution photoresist according to claim 2, wherein the temperature of the esterification reaction in S1 is 50-110 ℃ and the temperature of the reaction in S2 is 50-110 ℃.
7. The high resolution photoresist of claim 2, wherein the sulfite is sodium sulfite or potassium sulfite.
8. The high resolution photoresist according to claim 1, wherein the film forming resin is prepared from at least one acid reactive monomer having a specific general structural formula:
wherein R isaH or a carbon chain with 1-20 carbon atoms; rbIs an acid-sensitive quaternary carbon, RcH or a carbon chain with 1-20 carbon atoms; rdIs polar group-containing (meth) acrylate.
9. The high resolution photoresist of claim 8, wherein R isbThe catalyst is a quaternary ester with 6-30 carbon atoms, all hydrogen atoms of carbon atoms connected with hydroxyl oxygen atoms are substituted by other groups, and the structure of the quaternary ester is one or more of tert-butyl ester, substituted tert-butyl ester, alkyl-substituted adamantane derivative ester, alkyl-substituted norbornyl derivative ester, alkyl-substituted cyclic alkyl ester and alkyl-substituted cyclic alkyl derivative ester;
the R isdThe structure of the compound is one or more of adamantyl ester containing 1 or more independent hydroxyl groups, cyclohexyl ester containing 1 or more independent hydroxyl groups, cyclopentyl ester containing 1 or more independent hydroxyl groups, polycycloester compound containing 1 or more independent hydroxyl groups, caged ester compound containing 1 or more independent hydroxyl groups, butyrolactone, valerolactone, substituted valerolactone, caprolactone, substituted caprolactone, lactone containing a adamantane structure, lactone containing a polycyclic structure and lactone containing a caged structure.
10. The photoresist of claim 1, wherein the organic solvent A is one or more of methyl ether acetate, propylene glycol monoacetate, propylene glycol monoethyl ether, propylene glycol methyl ether acetate, diethylene glycol methyl ether, diethylene glycol diethyl ether, butyl acetate, neopentyl acetate, ethyl lactate, methyl ethyl ketone, cyclohexanone and methyl isobutyl ketone.
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| US20120164582A1 (en) * | 2009-09-11 | 2012-06-28 | Jsr Corporation | Radiation-sensitive composition and compound |
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| US20190243244A1 (en) * | 2016-10-13 | 2019-08-08 | Jsr Corporation | Radiation-sensitive resin composition and resist pattern-forming method |
| CN111221218A (en) * | 2020-02-28 | 2020-06-02 | 宁波南大光电材料有限公司 | Acid diffusion inhibitor, preparation method thereof and photoresist composition |
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