CN112764313A - Photoresist composition and preparation method thereof - Google Patents
Photoresist composition and preparation method thereof Download PDFInfo
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- CN112764313A CN112764313A CN202110089814.7A CN202110089814A CN112764313A CN 112764313 A CN112764313 A CN 112764313A CN 202110089814 A CN202110089814 A CN 202110089814A CN 112764313 A CN112764313 A CN 112764313A
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- photoresist composition
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- photoacid generator
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- 229920002120 photoresistant polymer Polymers 0.000 title claims abstract description 70
- 239000000203 mixture Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 31
- 238000009792 diffusion process Methods 0.000 claims abstract description 21
- 239000003112 inhibitor Substances 0.000 claims abstract description 21
- 150000005690 diesters Chemical group 0.000 claims abstract description 17
- 239000003960 organic solvent Substances 0.000 claims abstract description 17
- 239000011347 resin Substances 0.000 claims abstract description 17
- 229920005989 resin Polymers 0.000 claims abstract description 17
- 125000002887 hydroxy group Chemical group [H]O* 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 32
- 238000006243 chemical reaction Methods 0.000 claims description 24
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 239000003999 initiator Substances 0.000 claims description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 239000000178 monomer Substances 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 238000010438 heat treatment Methods 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
- 238000005886 esterification reaction Methods 0.000 claims description 5
- 150000002148 esters Chemical group 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 4
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 claims description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-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
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-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
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-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
- 239000003054 catalyst Substances 0.000 claims description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 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
- 238000001914 filtration Methods 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- 150000002978 peroxides Chemical class 0.000 claims description 4
- 150000003254 radicals Chemical group 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
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 4
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- 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
- HGXJDMCMYLEZMJ-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOOC(=O)C(C)(C)C HGXJDMCMYLEZMJ-UHFFFAOYSA-N 0.000 claims description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 claims description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-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
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-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
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-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
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 238000013329 compounding Methods 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
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- XCRBXWCUXJNEFX-UHFFFAOYSA-N peroxybenzoic acid Chemical compound OOC(=O)C1=CC=CC=C1 XCRBXWCUXJNEFX-UHFFFAOYSA-N 0.000 claims description 2
- 239000003208 petroleum Substances 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
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-N hydroperoxyl Chemical group O[O] OUUQCZGPVNCOIJ-UHFFFAOYSA-N 0.000 claims 1
- 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
- 239000000463 material Substances 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
- 238000005406 washing Methods 0.000 description 3
- 239000004677 Nylon Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000009826 distribution Methods 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
- 239000000243 solution Substances 0.000 description 2
- DNXHEGUUPJUMQT-CBZIJGRNSA-N Estrone Chemical compound OC1=CC=C2[C@H]3CC[C@](C)(C(CC4)=O)[C@@H]4[C@@H]3CCC2=C1 DNXHEGUUPJUMQT-CBZIJGRNSA-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
- 230000003321 amplification Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 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
- 239000011521 glass Substances 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
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000002868 norbornyl group Chemical group C12(CCC(CC1)C2)* 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 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
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 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
Images
Classifications
-
- 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
Abstract
The embodiment of the invention provides a photoresist composition and a preparation method thereof, wherein the photoresist composition 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, and the acid diffusion inhibitor is an acid diffusion inhibitor containing a hydroxyl functional unit and a basic functional unit. According to the photoresist composition provided by the embodiment of the invention, under the condition of adopting the photoacid generator containing a 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 containing the hydroxyl functional unit and the alkaline functional unit.
Description
Technical Field
The invention relates to the technical field of photoresist, in particular to a photoresist composition and a preparation method thereof.
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 photoresist composition and a preparation method thereof, wherein the photoresist composition adopts a photoacid generator containing a diester structure which is helpful for generating effective controllable large-volume acid in the photoresist to improve the line width and roughness of a circuit manufactured by using the photoresist, and simultaneously adopts an acid diffusion inhibitor containing a hydroxyl functional unit and a basic functional unit in the photoresist to further improve the resolution of the photoresist.
The embodiment of the invention provides a photoresist composition, 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;
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;
wherein, the specific structural general formula of the acid diffusion inhibitor is as follows:
wherein, R in the general formula (2)1、R2Is H or methyl, R3、R4One or more of alkyl with 1-40 hydrogen atoms and 1-20 carbon atoms, aryl or substituent containing sulfur/oxygen/nitrogen heteroatom, n is 5-200aIs one or more of an alkyl group, an aryl group or a functional structure containing a sulfur/oxygen/nitrogen heteroatom, nbIs a carbon chain containing one or more ether bonds and one or more ester bonds and having 1-20 carbon atoms, and contains naAnd the moiety of the hydroxyl structure is a hydroxyl functional unit comprising R3、R4And nbThe moiety of (a) is a basic functional unit.
Preferably, in the photoresist composition, 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.
More preferably, in the photoresist composition, the organic solvent B is one or more of toluene, dichloroethane or 4-dimethylaminopyridine; the catalyst is one or more of concentrated sulfuric acid and p-toluenesulfonic acid.
More preferably, in the photoresist composition, the alcohol organic compound is a saturated alcohol organic compound; the sulfite is sodium sulfite or potassium sulfite.
More preferably, in the photoresist composition, the temperature of the esterification reaction in S1 is 50-110 ℃ and the temperature of the reaction in S2 is 50-110 ℃.
Preferably, in the photoresist composition, the film-forming resin is prepared by at least one acid-reactive monomer, and the specific structural general 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 photoresist composition, R isbIs a quaternary ester with 6-30 carbon atoms, the hydrogen atoms of the carbon atoms connected with the oxygen atom of the hydroxyl group are all substituted by other groups, and the structure of the quaternary ester is tert-butyl ester, substituted tert-butyl ester, alkyl substituted adamantane derivative ester, alkyl substituted norbornyl ester and alkyl substituted norbornyl derivative esterOne or more of alkyl substituted cyclic alkyl ester and alkyl substituted cyclic alkyl derivative ester.
More preferably, in the photoresist composition, an initiator, an organic solvent C and a precipitant are added to the film-forming resin during the preparation process, wherein the initiator is a radical initiator of an azo initiator or a peroxide, the amount of the initiator is 0.3-15% of the total mass of the comonomer, the organic solvent C is 50-80% of the total mass of the comonomer, and the precipitant is 4-6 times of the total mass of the comonomer.
More preferably, in the photoresist composition, the azo initiator is one or more of azobisisobutyronitrile and azobisisoheptonitrile; the free radical initiator of the peroxide is one or more of tert-butyl peroxypivalate, tert-butyl hydroperoxide, benzoic acid hydroperoxide or benzoyl peroxide; the organic solvent C is one or more of methanol, ethanol, dioxane, acetone, methyl ethyl ketone, tetrahydrofuran, methyl tetrahydrofuran, benzene, toluene, xylene, chloroform, dichloroethane, trichloroethane and ethyl acetate; the precipitant is one or more of pure water, methanol/water mixture, ethanol/water mixture, isopropanol/water mixture, n-heptane, n-hexane, cyclohexane, n-pentane, petroleum ether, diethyl ether, and methyl tert-butyl ether.
Preferably, in the photoresist composition, 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.
The invention also provides a preparation method of the photoresist composition, which comprises the following steps: and mixing and dissolving the components, and then vibrating in a dark place, filtering the mixed solution after the vibration is finished, and collecting the filtrate, namely the photoresist composition.
According to the photoresist composition 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 acid diffusion inhibitor with ester bonds is adopted in the photoresist, so that the distribution of the acid diffusion inhibitor in the photoresist can be more effectively improved, 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 composition 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.
In the preparation process of the photoresist composition, the photoacid generator with the diester structure is adopted, so that after the photoresist is exposed, the photoacid generator with the diester structure in the photoresist generates effective and controllable large-volume acid, and shows excellent acid diffusion performance together with an acid inhibitor, the chemical amplification reaction is smoothly performed in an exposure area, the acid diffusion can be effectively inhibited at the joint of the exposure area and a non-exposure area, and the line roughness is greatly improved. In addition, the acid diffusion inhibitor containing a hydroxyl functional unit and an alkaline functional unit is added into the photoresist of the photoacid generator containing the diester structure, so that the distribution of the acid diffusion inhibitor in the photoresist can be more effectively improved, the resolution and the line width roughness of the photoresist are further improved, and the film forming capability of the photoresist is improved.
Example 1
A method for preparing a photoresist composition, the method comprising:
uniformly mixing 0.25g of a photoacid generator containing a diester structure, 8.5g of a film-forming resin, 0.06g of an acid diffusion inhibitor and 80g of an organic solvent A in a 100mL glass bottle, and carrying out light-shielding oscillation for 24 hours, filtering the mixed solution by using a 0.22 micrometer filter after the oscillation is finished, then filtering by using a 0.02 micrometer filter, and collecting the filtrate, namely the photoresist composition.
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 acid diffusion inhibitor has the structural formula:
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, wherein the mass ratio of the methyl ether acetate to the propylene glycol monoethyl ether is 2:3, the filter is made of a nylon material or a UPE material, and in the embodiment, the nylon material filter is preferred.
The photoresist composition prepared above is rotated to form a film on a No. 12 silicon wafer at the speed of 2500 rpm, then is baked for 90s on a hot plate at the temperature of 120 ℃, and is processed on an exposure machine at the exposure intensity of 45mJ/cm2The 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 which can be used for preparing high-resolution photoresist together with an acid diffusion inhibitor, thereby improving the resolution of the photoresist; the acid inhibitor contains hydroxyl to further increase the polarity and the solubility with resin, and further is uniformly dissolved with the photoacid generator, so that the adhesion 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 photoresist composition is characterized by 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, 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 in the general formula (1)1、R2Is the number of hydrogen atomsOne or more of an alkyl group having 1 to 40 carbon atoms, an aryl group, or a substituent containing a sulfur/oxygen heteroatom, and Q + is a sulfonium salt cation or an iodonium salt cation;
wherein, the specific structural general formula of the acid diffusion inhibitor is as follows:
wherein, R in the general formula (2)1、R2Is H or methyl, R3、R4One or more of alkyl with 1-40 hydrogen atoms and 1-20 carbon atoms, aryl or substituent containing sulfur/oxygen/nitrogen heteroatom, n is 5-200aIs one or more of an alkyl group, an aryl group or a functional structure containing a sulfur/oxygen/nitrogen heteroatom, nbIs a carbon chain containing one or more ether bonds and one or more ester bonds and having 1-20 carbon atoms, and contains naAnd the moiety of the hydroxyl structure is a hydroxyl functional unit comprising R3、R4And nbThe moiety of (a) is a basic functional unit.
2. The photoresist composition of claim 1, wherein the photoacid generator comprising 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 photoresist composition of claim 2, wherein the organic solvent B is one or more of toluene, dichloroethane, or 4-dimethylaminopyridine; the catalyst is one or more of concentrated sulfuric acid and p-toluenesulfonic acid; the alcohol organic compound is a saturated alcohol organic compound; the sulfite is sodium sulfite or potassium sulfite.
4. The photoresist composition of 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 ℃.
5. The photoresist composition of 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.
6. The photoresist composition of claim 5, wherein R isbThe quaternary ester is a C6-30 quaternary ester, 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.
7. The photoresist composition of claim 6, wherein an initiator, an organic solvent C and a precipitant are added in the preparation process of the film-forming resin, wherein the initiator is a radical initiator of an azo initiator or a peroxide, the amount of the initiator is 0.3-15% of the total mass of the comonomer, the organic solvent C is 50-80% of the total mass of the comonomer, and the precipitant is 4-6 times of the total mass of the comonomer.
8. The photoresist composition of claim 7, wherein the azo initiator is one or more of azobisisobutyronitrile, azobisisoheptonitrile; the free radical initiator of the peroxide is one or more of tert-butyl peroxypivalate, tert-butyl hydroperoxide, benzoic acid hydroperoxide or benzoyl peroxide; the organic solvent C is one or more of methanol, ethanol, dioxane, acetone, methyl ethyl ketone, tetrahydrofuran, methyl tetrahydrofuran, benzene, toluene, xylene, chloroform, dichloroethane, trichloroethane and ethyl acetate; the precipitant is one or more of pure water, methanol/water mixture, ethanol/water mixture, isopropanol/water mixture, n-heptane, n-hexane, cyclohexane, n-pentane, petroleum ether, diethyl ether, and methyl tert-butyl ether.
9. The photoresist composition 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.
10. A method for preparing a photoresist composition according to any one of claims 1 to 9, comprising the steps of: and mixing and dissolving the components, and then vibrating in a dark place, filtering the mixed solution after the vibration is finished, and collecting the filtrate, namely the photoresist composition.
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| CN113582846A (en) * | 2021-08-05 | 2021-11-02 | 安徽熙泰智能科技有限公司 | Photoresist monomer, preparation method thereof and photoresist |
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