CN113820918B - Photoacid generator for immersion ArF lithography and photoresist composition - Google Patents
Photoacid generator for immersion ArF lithography and photoresist composition Download PDFInfo
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- CN113820918B CN113820918B CN202110979405.4A CN202110979405A CN113820918B CN 113820918 B CN113820918 B CN 113820918B CN 202110979405 A CN202110979405 A CN 202110979405A CN 113820918 B CN113820918 B CN 113820918B
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- 229920002120 photoresistant polymer Polymers 0.000 title claims abstract description 64
- 239000000203 mixture Substances 0.000 title claims abstract description 53
- 238000007654 immersion Methods 0.000 title abstract description 8
- 238000001459 lithography Methods 0.000 title abstract description 5
- 150000001875 compounds Chemical class 0.000 claims description 42
- 239000002904 solvent Substances 0.000 claims description 29
- 125000000217 alkyl group Chemical group 0.000 claims description 24
- 239000011347 resin Substances 0.000 claims description 20
- 229920005989 resin Polymers 0.000 claims description 20
- 239000000654 additive Substances 0.000 claims description 13
- 230000000996 additive effect Effects 0.000 claims description 12
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical group [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 7
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 4
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 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
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical group COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical group CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 2
- 230000035945 sensitivity Effects 0.000 abstract description 8
- 239000002253 acid Substances 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 description 21
- 125000003118 aryl group Chemical group 0.000 description 19
- 238000000034 method Methods 0.000 description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 11
- 150000003839 salts Chemical class 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- HTSGKJQDMSTCGS-UHFFFAOYSA-N 1,4-bis(4-chlorophenyl)-2-(4-methylphenyl)sulfonylbutane-1,4-dione Chemical compound C1=CC(C)=CC=C1S(=O)(=O)C(C(=O)C=1C=CC(Cl)=CC=1)CC(=O)C1=CC=C(Cl)C=C1 HTSGKJQDMSTCGS-UHFFFAOYSA-N 0.000 description 8
- 238000005755 formation reaction Methods 0.000 description 8
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- -1 anthracyl Chemical group 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000005886 esterification reaction Methods 0.000 description 6
- 238000000206 photolithography Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 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 description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000012074 organic phase Substances 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- FKLJPTJMIBLJAV-UHFFFAOYSA-N Compound IV Chemical compound O1N=C(C)C=C1CCCCCCCOC1=CC=C(C=2OCCN=2)C=C1 FKLJPTJMIBLJAV-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 150000005840 aryl radicals Chemical class 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 238000001259 photo etching Methods 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 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 3
- 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 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 239000006117 anti-reflective coating Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000005459 micromachining Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 125000005561 phenanthryl group Chemical group 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- KQPQZWKCUWVZDD-UHFFFAOYSA-N 1-methyladamantane;prop-2-enoic acid Chemical compound OC(=O)C=C.C1C(C2)CC3CC2CC1(C)C3 KQPQZWKCUWVZDD-UHFFFAOYSA-N 0.000 description 1
- ZAIZJZXPWYLNLE-UHFFFAOYSA-N 2-bromo-2,2-difluoroethanol Chemical compound OCC(F)(F)Br ZAIZJZXPWYLNLE-UHFFFAOYSA-N 0.000 description 1
- YMPABRCXIUBTJZ-UHFFFAOYSA-N 3-(5-bicyclo[2.2.1]hept-2-enyl)-3-hydroxypropanoic acid Chemical compound C1C2C(C(CC(O)=O)O)CC1C=C2 YMPABRCXIUBTJZ-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- JJHHIJFTHRNPIK-UHFFFAOYSA-N Diphenyl sulfoxide Chemical compound C=1C=CC=CC=1S(=O)C1=CC=CC=C1 JJHHIJFTHRNPIK-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- IWCVDCOJSPWGRW-UHFFFAOYSA-M magnesium;benzene;chloride Chemical compound [Mg+2].[Cl-].C1=CC=[C-]C=C1 IWCVDCOJSPWGRW-UHFFFAOYSA-M 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- 239000012953 triphenylsulfonium Substances 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Materials For Photolithography (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses an immersion type photo-acid generator for ArF lithography and a photoresist composition. The photoacid generator is shown in formula I. The photoresist containing the photoacid generator has the advantages of high resolution, high sensitivity and low line width roughness, and has good application prospect.
Description
Technical Field
The invention relates to an immersion type photo-acid generator for ArF lithography and a photoresist composition.
Background
The photolithography technique refers to a pattern micromachining technique for transferring a pattern designed on a mask plate onto a substrate through exposure, development, etching and other technological processes by utilizing chemical sensitivity of a photolithography material (particularly photoresist) under the actions of visible light, ultraviolet rays, electron beams and the like. Photolithography materials (particularly photoresists), also known as photoresists, are the most critical functional chemical materials involved in photolithography, the main components of which are resins, photoacid generators (Photo Acid Generator, PAG), and corresponding additives and solvents. The photoacid generator is a photosensitive compound which is decomposed under illumination to generate acid, and the generated acid can lead acid-sensitive resin to generate decomposition or crosslinking reaction, so that the dissolution contrast of an illumination part and a non-illumination part in a developing solution is increased, and the photoacid generator can be used in the technical field of pattern micromachining.
Three important parameters of photoresist include resolution, sensitivity, line width roughness, which determine the process window of the photoresist at the time of chip fabrication. With the continuous improvement of the performance of semiconductor chips, the integration level of integrated circuits increases exponentially, and the patterns in the integrated circuits continue to shrink. In order to make smaller sized patterns, the performance index of the above three photoresists must be improved. The use of a short wavelength light source in the photolithography process may increase the resolution of the photoresist according to the rayleigh equation. The light source wavelength of the photolithography process has evolved from 365nm (I-line) to 248nm (KrF), 193nm (ArF), 13nm (EUV). In order to improve the sensitivity of the photoresist, the currently mainstream KrF, arF, EUV photoresist adopts a chemically amplified photosensitive resin. Thus, photosensitizers (photoacid generators) compatible with chemically amplified photosensitive resins are widely used in high-end photoresists.
With the gradual development of the photoetching process, the immersion process of 193nm is adopted, the process complexity is increased, and the requirements on the photoacid generator are increased. Development of a photoacid generator capable of improving resolution, sensitivity and line width roughness of photoresist becomes a problem to be solved urgently in the industry.
Disclosure of Invention
The invention aims to overcome the defect of few types of photoacid generators matched with chemical amplification type photosensitive resin in the prior art, and provides a photoacid generator for immersion ArF lithography and a photoresist composition. The photoresist containing the photoacid generator has the advantages of high resolution, high sensitivity and low line width roughness.
The invention solves the technical problems through the following technical proposal.
The invention provides application of a compound shown as a formula I in photoresist as a photoacid generator;
wherein R is 1 、R 2 、R 3 、R 4 And R is 5 Independently H, halogen, C 1-6 Alkyl or-O-C 1-6 An alkyl group;
n is 2 or 3;
a is S or I;
y is C 6-14 Aryl, quilt Y -1 Substituted C 6-14 Aryl (Y) -1 1 or more, for example 1, 2 or 3; when Y is -1 When there are a plurality of Y -1 Identical or different) or
Y -1 Is hydroxy, C 1-6 Alkyl or-O-C 1-6 An alkyl group;
m is C 6-14 Aryl, quilt M -1 Substituted C 6-14 Aryl (M) -1 1 or more, for example 1, 2 or 3; when M -1 When there are a plurality of M -1 Identical or different) or not (i.e. not presentIs->);
M -1 Independently C 1-6 Alkyl or-O-C 1-6 An alkyl group.
In some embodiments, R 1 、R 2 、R 3 、R 4 And R is 5 Wherein the halogen is F, cl, br or I.
In some embodiments, R 1 、R 2 、R 3 、R 4 And R is 5 In (C) 1-6 Alkyl and said-O-C 1-6 C in alkyl 1-6 Alkyl is independently methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl.
In some embodiments, Y is said C 6-14 Aryl and said quilt Y -1 Substituted C 6-14 C in aryl group 6-14 Aryl is independently phenyl, naphthyl, phenanthryl or anthracyl, e.g. phenyl.
In some embodiments, Y -1 In (C) 1-6 Alkyl and said-O-C 1-6 C of alkyl groups 1-6 Alkyl is independently methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl, for example n-propyl.
In some embodiments, Y is said to be Y -1 Substituted C 6-14 Aryl radicals being
In some embodiments, when said Y is said C 6-14 Aryl or said quilt Y -1 Substituted C 6-14 Aryl, said C 6-14 Aryl and said quilt Y -1 Substituted C 6-14 C in aryl group 6-14 When aryl is independently phenyl, saidIs that
In some embodiments, M is the same as C 6-14 Aryl and quilt M -1 Substituted C 6-14 C in aryl group 6-14 Aryl is independently phenyl, naphthyl, phenanthryl or anthracyl, for example phenyl.
In some embodiments, M -1 In (C) 1-6 Alkyl and said-O-C 1-6 C in alkyl 1-6 Alkyl is independently methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl, for example methyl.
In some embodiments, in M, said quilt M -1 Substituted C 6-14 Aryl radicals being
In some embodiments, R 1 、R 2 、R 3 、R 4 And R is 5 H.
In some embodiments, n is 3.
In some embodiments, a is S.
In some embodiments, Y -1 Is hydroxy or-O-C 1-6 An alkyl group.
In some embodiments, M -1 Independently C 1-6 An alkyl group.
In some of the embodiments of the present invention,is->
In some embodiments, Y is
In some embodiments, R 1 、R 2 、R 3 、R 4 And R is 5 Is H;
n is 3;
a is S;
y is C 6-14 Aryl, quilt Y -1 Substituted C 6-14 Aryl or aryl radicals
Y -1 Is hydroxy or-O-C 1-6 An alkyl group;
m is C 6-14 Aryl, quilt M -1 Substituted C 6-14 Aryl or absent;
M -1 independently C 1-6 An alkyl group.
In some embodiments, the compound of formula I is any one of the following:
the invention also provides a photoresist composition, which comprises the following raw materials: the compound shown in the formula I, the resin shown in the formula (1), the alkaline additive and the solvent;
in the photoresist composition, the parts by weight of the compound shown in formula I are preferably 2-10 parts, for example 4 parts.
In the photoresist composition, the resin represented by the formula (1) is preferably 20 to 120 parts by weight, for example, 100 parts by weight.
In the photoresist composition, the weight average molecular weight of the resin represented by the formula (1) is preferably 8000 to 9000g/mol, for example 8500g/mol.
In the photoresist composition, the alkali additive is preferably 0.1 to 1 part, for example, 0.5 part, by weight.
The alkaline additive in the photoresist composition can be conventional in the art, preferably C 1-4 Alkyl quaternary ammonium bases such as tetramethyl ammonium hydroxide.
In the photoresist composition, the solvent is preferably 500 to 2000 parts by weight, for example, 1000 parts by weight.
In the photoresist composition, the solvent may be a solvent conventional in the art, preferably an ester solvent such as propylene glycol methyl ether acetate.
The photoresist composition comprises the following raw materials in parts by weight: 4 parts of the compound shown in the formula I, 100 parts of the resin shown in the formula (1), 0.5 part of an alkaline additive and 1000 parts of a solvent.
The photoresist composition consists of the following raw materials: the compound shown as the formula I, the resin, the alkaline additive and the solvent.
The invention also provides a preparation method of the photoresist composition, which comprises the following steps: mixing the above materials uniformly.
In the preparation method, the mixing mode can be a mixing mode conventional in the field, and vibration is preferred.
In the preparation method, the mixing step preferably further comprises filtration with a filter membrane, for example, a 0.2 μm filter membrane.
The invention also provides application of the photoresist composition in a photoetching process.
Wherein, the photoetching process preferably comprises the following steps: the photoresist composition is applied to a pretreated substrate, dried (e.g., at 110 ℃ for 90 seconds), exposed to light, and developed (e.g., using a developer solution that is an aqueous solution of tetramethylammonium hydroxide).
The invention provides a compound shown in the formula I:
wherein R is 1 、R 2 、R 3 、R 4 、R 5 The definitions of n and Y are the same as described above.
The invention also provides a preparation method of the compound shown in the formula I, which comprises the following steps:
in a solvent, carrying out salt forming reaction of a compound II and a compound III in the solvent to obtain a compound shown in the formula I;
wherein X is halogen; n is an alkali metal.
In X, the halogen is preferably F, cl, br or I, such as Cl.
In N, the alkali metal is preferably Li, na or K, for example Na.
The salt-forming reaction may be a conventional reaction in the art of salifying onium salts with sulfonic acid anions, and the present invention particularly preferably operates under the following conditions:
in the salt forming reaction, the solvent can be an alcohol solvent and water. The alcohol solvent can be methanol, ethanol, n-propanol or isopropanol, and can further be methanol. The volume ratio of the alcohol solvent to the water is 0.8:1 to 1.5:1, for example 1.0:1.
In the salt-forming reaction, the molar ratio of the compound III to the compound II may be 1.5:1 to 2.5:1, for example 2.0:1.
In the salt formation reaction, the compound II is preferably added to the solution containing the compound II in the form of an aqueous solution.
The salification reaction can be carried out under the condition of avoiding light.
The temperature of the salt formation reaction may be 5-40 ℃, for example room temperature.
The progress of the salt formation reaction can be monitored by methods conventional in the art (e.g., TLC) with the compound III no longer reacting as an endpoint of the reaction. The salt formation reaction may take from 8 to 24 hours, for example 12 hours.
The post-treatment step of the salt formation reaction may be a conventional post-treatment step of such salt formation reaction in the art, preferably extraction. The solvent for extraction may be a halogenated hydrocarbon solvent (e.g., chloroform). The number of extractions may be 2-3, for example 3.
The preparation method of the compound shown in the formula I can further comprise the following steps:
step 1, in the presence of an alkaline reagent and a compound IV, reacting a compound III in a solvent to obtain a mixture;
step 2, in the presence of hydrogen peroxide, reacting the mixture obtained in the step 1 in water to obtain the compound II;
in step 1, the alkaline agent may be an alkaline agent conventional in the art, preferably an alkali metal carbonate and/or alkali metal bicarbonate (e.g., sodium bicarbonate).
In step 1, the molar ratio of the basic reagent to the compound III may be conventional in the art, preferably 1.5:1 to 4.0:1, for example 3.0:1.
In step 1, the molar ratio of said compound IV to said compound III may be a molar ratio conventional in the art, preferably 1.5:1 to 2.5:1, for example 2.0:1.
In step 1, the solvent may be a solvent conventional in such reactions in the art, preferably a nitrile solvent (e.g., acetonitrile) and water. The volume ratio of the nitrile solvent to the water is 0.8:1 to 1.2:1, e.g., 1.0:1.
In step 1, the temperature of the oxidation reaction may be 50-90 ℃, for example 70 ℃.
In step 1, the time of the oxidation reaction may be 8 to 24 hours, for example, 16 hours.
In step 2, the molar ratio of the compound hydrogen peroxide to the compound III may be a molar ratio conventional in the art, preferably 1.5:1 to 3.0:1, for example 2.0:1.
In step 2, the temperature of the oxidation reaction may be 5-40 ℃, for example, room temperature.
In step 2, the time of the oxidation reaction may be 8 to 24 hours, for example, 16 hours.
The preparation method of the compound shown in the formula I can further comprise the following steps: in the presence of p-toluenesulfonic acid, carrying out esterification reaction of a compound V and a compound VI in a solvent to obtain a compound II;
the esterification reaction may be conventional in the art, and the present invention particularly preferably employs the following conditions and operations:
in the esterification reaction, the molar ratio of the p-toluenesulfonic acid to the compound VI may be in the range of 0.1:1 to 0.3:1, for example 0.22:1.
In the esterification reaction, the molar ratio of the compound VI to the compound VI may be 2.0:1 to 4.0:1, for example 3.0:1.
In the esterification reaction, the solvent may be an aromatic solvent (e.g., toluene).
The temperature of the esterification reaction may be 110-130 ℃, for example room temperature.
The progress of the salt formation reaction can be monitored by methods conventional in the art (e.g., TLC) with the compound IV no longer reacting as an endpoint of the reaction. The salt formation reaction may take from 5 to 10 hours, for example 9 hours.
The post-treatment step of the salification reaction may be a conventional post-treatment step of such salification reaction in the art, preferably alkali washing (e.g., 3 times), saturated saline washing (e.g., 1 time), and drying (e.g., anhydrous sodium sulfate drying).
The invention also provides a compound II:
wherein Y and N are as defined above.
The compound II is any one of the following compounds:
in the present invention, "room temperature" means 10 to 25 ℃.
The above preferred conditions can be arbitrarily combined on the basis of not deviating from the common knowledge in the art, and thus, each preferred embodiment of the present invention can be obtained.
The reagents and part of raw materials used in the invention are commercially available, and part of raw materials are self-made.
The invention has the positive progress effects that: the photoresist prepared by adopting the photoacid generator has the advantages of high resolution, high sensitivity and low line width roughness.
Detailed Description
The invention is further illustrated by means of the following examples, which are not intended to limit the scope of the invention. The experimental methods, in which specific conditions are not noted in the following examples, were selected according to conventional methods and conditions, or according to the commercial specifications.
Preparing raw materials:
the above starting materials were prepared according to the preparation method of example 1 in CN105399602 a.
The above starting materials were prepared according to the preparation method of example 1 in CN109485573 a.
Preparation of the resin
In the examples or comparative examples of the present invention, the resin was prepared as follows:
in a molar ratio of 1:1:1 to 3-bicyclo [2.2.1] hept-5-en-2-yl-3-hydroxypropionate (hereinafter referred to as BHP), 1-methyladamantane acrylate and gamma-butyrolactone acrylate. 1, 4-dioxane was added in an amount of 300 parts by weight with respect to 100 parts by weight of the total amount of the reaction monomers as a polymerization solvent, azobisisobutyronitrile was added in an amount of 4 parts by mole with respect to 100 parts by weight of the total amount of the reaction monomers as an initiator, and the mixture was reacted at 65℃for 16 hours.
After the reaction, the reaction solution was precipitated with n-hexane, and the precipitate was removed and dried in vacuo. Thus, a resin represented by the following formula (1) was obtained, which had a weight average molecular weight of about 8500g/mol.
Example 1
Step 1: synthesis of Compound III-1
A250 mL glass bottle equipped with an oil-water separator and a condenser was charged with 2-bromo-2, 2-difluoroethanol (24.1 g,0.15mol,3.0 eq), compound V-1 (17.3 g,0.05mol,1.0 eq), p-toluenesulfonic acid (1.7 g,0.01mol,0.2 eq) and 80mL toluene, and the mixture was heated under reflux with stirring for 8h. After completion of the reaction, the reaction mixture was cooled, washed 3 times with 50mL of an aqueous sodium carbonate solution, washed 1 time with 50mL of a saturated brine, and the organic phase was dried over anhydrous sodium sulfate, and concentrated to give 16.2g of an intermediate in total, the yield was 51.2%.
LC-MS:631.8.
Step 2: synthesis of Compound II-1
In a 500mL round bottom flask, compound II-1 (16.0 g,0.025mol,1.0 eq) and 80mL acetonitrile were added and dissolved with stirring. Under the protection of nitrogen, 80mL of an aqueous solution containing sodium dithionite (8.8 g,0.051mol,2.0 eq) and sodium bicarbonate (6.38 g,0.076mol,3.0 eq) was added dropwise, and after the addition was completed, the reaction solution was heated and stirred at 70℃for 16 hours. After the reaction was completed, it was cooled and a proper amount of sodium chloride solid was added until the solution was saturated. The reaction was separated and the aqueous phase was extracted 2 times with 30mL of acetonitrile. The organic phases were combined and transferred to a 500mL round bottom flask, and 100mL of pure water was added. The mixture was added dropwise with 30% hydrogen peroxide (5.7 g,0.051mol,2.0 eq) under nitrogen, and then stirred at room temperature for 16h. After the completion of the reaction, the mixture was separated into layers, the aqueous phase was extracted 2 times with 50mL of acetonitrile, the organic phase was dried over anhydrous sodium sulfate, and concentrated to give compound II-1.9 g, the yield was 69.3%.
1 HNMR(400MHz,DMSO):δppm:2.45,6H;4.82,4H;7.41,1H;7.75-7.91,9H.
Step 3: synthesis of Compound I-1
Triphenylsulfonium chloride synthesis
Diphenylsulfoxide (6.0 g,0.030mol,1.0 eq) and 60mL of anhydrous methylene chloride were added dropwise to a 250mL three-necked flask at a temperature below 0deg.C under nitrogen protection, and trimethylchlorosilane (9.6 g,0.090mol,3.0 eq) was added dropwise. After the dripping is finished, the temperature is slowly raised to the room temperature, and stirring is continued for 1h. Then, the reaction mixture was cooled to 0℃or lower again, and at this temperature, a tetrahydrofuran solution (45 ml/2M,0.090mol,3.0 eq) of phenylmagnesium chloride was added dropwise. After the dripping is finished, the temperature is slowly raised to the room temperature, and stirring is continued for 2 hours. The reaction mixture was quenched with a small amount of water, and 75mL of a 0.2N aqueous hydrochloric acid solution was added. After the mixed solution is washed twice with 30mL of diethyl ether, the water phase is the aqueous solution of triphenylsulfonium chloride salt, and the aqueous solution is placed in a dark place for standby.
Synthesis of Compound I-1
A250 mL round bottom flask was charged with Compound II-1 (10.0 g,0.014mol,1.0 eq) and 70mL methanol, and dissolved with stirring. Then, an aqueous solution (0.030 mmol,2.0 eq) of a previously prepared triphenylsulfonium chloride salt was added dropwise under light-protected conditions. After the dripping is finished, stirring for 16 hours in a dark place is continued. After the completion of the extraction, 30mL of chloroform was used for 3 times, and the organic phases were combined and washed with 30mL of pure water 2 times. The aqueous phase was removed by separation and the organic phase was concentrated to give compound I-1.1 g in 47.4% yield.
1 HNMR(400MHz,DMSO):δppm:2.45,6H;4.82,4H;7.28-7.36,31H;7.70-8.04,9H.
Examples 2 to 6
The compounds of examples 2-6 were prepared as described in reference to example 1. The starting materials, intermediate compounds II and compounds I used are shown in tables 1 and 2, respectively.
TABLE 1
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TABLE 2
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Example 7 preparation of Photoresist composition and comparative Photoresist composition
The photoresist composition of the present invention and the comparative photoresist composition were prepared as follows:
100 parts by weight of the resin prepared as above, 0.5 parts by weight of tetramethylammonium hydroxide (as an alkaline additive), and 4 parts by weight of the photoacid generator according to Table 3 were dissolved in 1000 parts by weight of propylene glycol methyl ether acetate, and then the solution was filtered through a 0.2- μm membrane filter, thereby preparing a photoresist composition. Among them, photoacid generators in the photoresist compositions of examples 1 to 6 and comparative examples 1 to 14 are shown in table 3.
TABLE 3 Table 3
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Comparative Compound 1 bis-triphenylsulfonium salt bis (2-sulfonic acid-2, 2-difluoroethoxy) succinate
The preparation of bis (triphenylsulfonium salt) bis (2-sulfonic acid-2, 2-difluoroethoxy) succinate was carried out in the same manner as in example 1.
1 HNMR(400MHz,DMSO):δppm:2.68,4H;4.95,4H;7.22-7.40,30H.
Comparative Compounds 2-14
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Comparative compounds 2-9 were prepared according to step 2 and step 3 of example 1.
Comparative compounds 10-14 were prepared as in example 1.
Application and effects examples
An anti-reflective coating ARC-29 (Nissan Chemical Industries, ltd.) was coated on a silicon wafer (12 inches) using a spin coater, then baked at 205 ℃ for 60 seconds to form an organic anti-reflective coating layer 70nm thick, then the prepared photoresist composition was coated, and dried at 110 ℃ for 90 seconds to form a film having a thickness of 0.20 μm. The resulting structure was exposed to light using an immersion exposure apparatus (1700 i, manufactured by ASML co.) and baked at 105 ℃ for 60 seconds. Thereafter, the film was developed with 2.38 wt% aqueous tetramethylammonium hydroxide solution for 40 seconds, and washed and dried. Thereby forming a photoresist pattern using ultrapure water as an immersion medium.
After development, the following development will be described with 1:1 to form a line-and-space (L/S) pattern of 0.10 μm, and the optimum exposure was designated as sensitivity (unit: mJ/cm) 2 ). The minimum pattern size resolved at this time is designated as resolution (unit: nm).
Further, in the case of Line Edge Roughness (LER), pattern roughness in a line pitch (L/S) pattern of 0.10 μm formed after development was observed, and LER (smaller value indicates better LER) (unit: nm) was measured.
The effects of the photoresist compositions of examples 1 to 6 and comparative example are shown in Table 4.
TABLE 4 Table 4
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Claims (10)
1. The application of a compound shown as a formula I as a photoacid generator in photoresist;
wherein R is 1 、R 2 、R 3 、R 4 And R is 5 Independently H, halogen, C 1-6 Alkyl or-O-C 1-6 An alkyl group;
n is 2 or 3;
a is S or I;
y is
2. The use according to claim 1, wherein the compound of formula I satisfies 1 or 2 of the following conditions:
①R 1 、R 2 、R 3 、R 4 and R is 5 Wherein the halogen is F, cl, br or I;
②R 1 、R 2 、R 3 、R 4 and R is 5 In (C) 1-6 Alkyl and said-O-C 1-6 C in alkyl 1-6 Alkyl is independently methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl.
3. The use according to claim 1, wherein the compound of formula I satisfies one or more of the following conditions:
①R 1 、R 2 、R 3 、R 4 and R is 5 Is H;
(2) n is 3;
(3) a is S.
4. The use according to claim 1, wherein,is->
5. The use according to claim 1, wherein R 1 、R 2 、R 3 、R 4 And R is 5 Is H;
n is 3;
a is S;
y is
6. The use according to claim 1, wherein the compound of formula I is any one of the following compounds:
7. a photoresist composition comprising the following raw materials: the compound according to any one of claims 1 to 6, represented by formula I, a resin represented by formula (1), a basic additive and a solvent;
8. the photoresist composition of claim 7, wherein the photoresist composition satisfies one or more of the following conditions:
(1) in the photoresist composition, the parts by weight of the compound shown in the formula I are 2-10 parts;
(2) in the photoresist composition, the resin shown in the formula (1) is 20-120 parts by weight;
(3) in the photoresist composition, the weight average molecular weight of the resin shown in the formula (1) is 8000-9000g/mol;
(4) in the photoresist composition, the alkaline additive is 0.1-1 part by weight;
(5) the alkaline additive in the photoresist composition is C 1-4 Alkyl quaternary ammonium base;
(6) in the photoresist composition, the solvent is 500-2000 parts by weight;
(7) in the photoresist composition, the solvent is an ester solvent.
9. The photoresist composition of claim 8, wherein the photoresist composition satisfies one or more of the following conditions:
(1) in the photoresist composition, the parts by weight of the compound shown in the formula I are 4 parts;
(2) in the photoresist composition, the resin shown in the formula (1) is 100 parts by weight;
(3) in the photoresist composition, the weight average molecular weight of the resin shown in the formula (1) is 8500g/mol;
(4) in the photoresist composition, the alkaline additive is 0.5 part by weight;
(5) in the photoresist composition, the alkaline additive is tetramethyl ammonium hydroxide;
(6) in the photoresist composition, the solvent is 1000 parts by weight;
(7) in the photoresist composition, the solvent is propylene glycol methyl ether acetate.
10. The photoresist composition of any one of claims 7 to 9, wherein the photoresist composition consists of: the compound shown as the formula I, the resin, the alkaline additive and the solvent.
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