CN116162186A - Acid generator based on polystyrene sulfonium salt and photoresist composition thereof - Google Patents
Acid generator based on polystyrene sulfonium salt and photoresist composition thereof Download PDFInfo
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- CN116162186A CN116162186A CN202111407327.7A CN202111407327A CN116162186A CN 116162186 A CN116162186 A CN 116162186A CN 202111407327 A CN202111407327 A CN 202111407327A CN 116162186 A CN116162186 A CN 116162186A
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- polymer
- photoresist
- alkyl
- lithography
- sulfonium salt
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- 229920002120 photoresistant polymer Polymers 0.000 title claims abstract description 53
- 239000002253 acid Substances 0.000 title claims abstract description 31
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 239000000203 mixture Substances 0.000 title claims description 19
- 239000004793 Polystyrene Substances 0.000 title description 9
- 229920002223 polystyrene Polymers 0.000 title description 9
- 229920000642 polymer Polymers 0.000 claims abstract description 49
- 238000000034 method Methods 0.000 claims abstract description 10
- -1 tetrafluoroborate Chemical compound 0.000 claims description 24
- 125000000217 alkyl group Chemical group 0.000 claims description 22
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 10
- 238000001459 lithography Methods 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 229910052717 sulfur Inorganic materials 0.000 claims description 8
- WJKHJLXJJJATHN-UHFFFAOYSA-N triflic anhydride Chemical compound FC(F)(F)S(=O)(=O)OS(=O)(=O)C(F)(F)F WJKHJLXJJJATHN-UHFFFAOYSA-N 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 7
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 7
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 6
- 125000000524 functional group Chemical group 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 239000011593 sulfur Substances 0.000 claims description 6
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 150000001450 anions Chemical class 0.000 claims description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 4
- 238000000609 electron-beam lithography Methods 0.000 claims description 4
- 125000000623 heterocyclic group Chemical group 0.000 claims description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 4
- FUGYGGDSWSUORM-UHFFFAOYSA-N 4-hydroxystyrene Chemical group OC1=CC=C(C=C)C=C1 FUGYGGDSWSUORM-UHFFFAOYSA-N 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- XBWQFDNGNOOMDZ-UHFFFAOYSA-N 1,1,2,2,3,3,3-heptafluoropropane-1-sulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)F XBWQFDNGNOOMDZ-UHFFFAOYSA-N 0.000 claims description 2
- MZVABYGYVXBZDP-UHFFFAOYSA-N 1-adamantyl 2-methylprop-2-enoate Chemical compound C1C(C2)CC3CC2CC1(OC(=O)C(=C)C)C3 MZVABYGYVXBZDP-UHFFFAOYSA-N 0.000 claims description 2
- HCFAJYNVAYBARA-UHFFFAOYSA-N 4-heptanone Chemical compound CCCC(=O)CCC HCFAJYNVAYBARA-UHFFFAOYSA-N 0.000 claims description 2
- 150000008052 alkyl sulfonates Chemical class 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 238000001900 extreme ultraviolet lithography Methods 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims description 2
- 238000001127 nanoimprint lithography Methods 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- JGTNAGYHADQMCM-UHFFFAOYSA-N perfluorobutanesulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F JGTNAGYHADQMCM-UHFFFAOYSA-N 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 238000006467 substitution reaction Methods 0.000 claims description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium group Chemical group [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 claims description 2
- 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 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 claims description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 2
- 230000004927 fusion Effects 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 9
- LDYNSPRLHCXFQC-UHFFFAOYSA-N styrene;sulfane Chemical compound S.C=CC1=CC=CC=C1 LDYNSPRLHCXFQC-UHFFFAOYSA-N 0.000 abstract description 5
- 238000010521 absorption reaction Methods 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000000276 deep-ultraviolet lithography Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 238000000233 ultraviolet lithography Methods 0.000 abstract description 2
- 239000002798 polar solvent Substances 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 9
- 239000000758 substrate Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 5
- 238000009472 formulation Methods 0.000 description 5
- 238000004528 spin coating Methods 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000003321 amplification Effects 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000010894 electron beam technology Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 238000003199 nucleic acid amplification method Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 238000001259 photo etching Methods 0.000 description 2
- 238000000206 photolithography Methods 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 125000005918 1,2-dimethylbutyl group Chemical group 0.000 description 1
- 125000006218 1-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 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 1
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- 125000005916 2-methylpentyl group Chemical group 0.000 description 1
- 125000003542 3-methylbutan-2-yl group Chemical group [H]C([H])([H])C([H])(*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000005917 3-methylpentyl group Chemical group 0.000 description 1
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 1
- 125000005915 C6-C14 aryl group Chemical group 0.000 description 1
- 239000004215 Carbon black (E152) Substances 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
- 239000003513 alkali Substances 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical class I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- WLOQLWBIJZDHET-UHFFFAOYSA-N triphenylsulfonium Chemical class C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 WLOQLWBIJZDHET-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
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- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/34—Introducing sulfur atoms or sulfur-containing groups
-
- 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
- C08F112/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F112/02—Monomers containing only one unsaturated aliphatic radical
- C08F112/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F112/06—Hydrocarbons
- C08F112/08—Styrene
-
- 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
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Materials For Photolithography (AREA)
Abstract
The invention discloses a styrene sulfonium salt polymer containing a repeating unit shown in the following formula (I), which has simple synthesis process and cheap and easily available raw materials. The polymer has good solubility in various polar solvents and good film forming property, can be used as an acid generator for photoresist, can avoid the problems of poor solubility and poor film forming property of a small molecular acid generator, and has better compatibility with a photoresist main body material. By changing the sulfonium salt structure, the sulfonium salt has long absorption wavelength and can be used for ultraviolet lithography and deep ultraviolet lithography.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a polymer acid generator based on polystyrene sulfonium salts and a photoresist composition thereof.
Background
With the rapid development of the semiconductor industry, the integration level of semiconductor devices is higher and higher, the resolution achieved by the requirements of photolithography technology is higher and higher requirements are also put on the quality of high-resolution photolithography patterns, and particularly, the requirements on Line Width Roughness (LWR) and Line Edge Roughness (LER) of patterns are more and more severe. Photoresist is a critical material for lithographic pattern transfer during semiconductor device processing. The photoresist is coated on different substrates, after energy radiation such as light beams, electron beams, ion beams or x rays is carried out, the solubility is changed, the corresponding patterns are transferred onto the substrates through development and etching processes, the resolution ratio achieved by the patterns formed by the photoresist has a determining influence on the integration level of devices, and the comprehensive performance of the photoresist needs to be matched with the development of the current photoetching technology.
Currently, conventional high resolution photoresists employ chemical amplification, the concept of "chemical amplification" was proposed by IBM corporation in 1982, where photoacid generator (Photo Acid Generator, PAG) is a key component in the photoresist composition. The term "chemical amplification" refers to that the PAG is decomposed to generate acid after illumination, the acid initiates a series of chemical reactions, so that the solubility of the photoresist material in the illumination area and the non-illumination area is obviously changed, and then pattern transfer can be realized through development, so that the acid generation efficiency of the photoacid generator and the distribution uniformity of the acid generator in the material have important effects on the pattern quality.
Common acid generators are largely divided into ionic acid generators, such as sulfonium salts, iodonium salts, and nonionic acid generators. These acid generators are usually small molecules, which are usually poorly soluble and poorly compatible with the polymeric host material, resulting in uneven distribution of the acid generator in the host material, resulting in reduced photoresist resolution and increased line edge roughness. Compared with the prior art, the high molecular acid generator has similar structure with the main material of the photoresist and better compatibility, thereby ensuring that the acid generator is distributed more uniformly in the photoresist. Thereby, the resolution of the photoresist can be improved and the line edge roughness of the photoresist can be reduced.
Disclosure of Invention
In order to solve the technical problems, the invention firstly provides a sulfonium salt polymer of styrene, wherein the repeating unit of the polymer has a structure shown in the following formula (I):
wherein: x and y represent the content percentages of the two monomers in the polymer, x+y=1, 0 < x < 0.3; x is, for example, 0.17, 0.25; y is, for example, 0.75, 0.83;
R 1 selected from sulfonium salt groups; r is R 1 The position of (c) may be para, meta or ortho; r is R 2 Selected from H, OH, halogen (Cl, F, I), C 1-15 Alkyl, C 1-15 Alkoxy, aryl; q is selected from integers from 1 to 5, preferably from 1 to 3;
X – is an anion, for example selected from the group consisting of halide, alkyl sulfonate, haloalkylsulfonate (e.g., triflate, perfluoropropyl sulfonate, perfluorobutyl sulfonate), p-toluenesulfonate, tetrafluoroborate, hexafluorophosphate, bis-trifluoromethanesulfonyl imide.
According to an embodiment of the invention, the R 1 is-S + R 3 R 4, wherein ,R3 、R 4 Identical or different, independently selected from C 1-15 Alkyl, deuterated C 1-15 Alkyl (e.g. deuteromethyl), aryl, or R 3 、R 4 And S attached thereto form a 5-8 membered sulfur-containing heterocyclic group, optionally further containing 1-2 oxygen or sulfur, optionally fused to one or two benzene rings; the alkyl, aryl, sulfur-containing heterocyclyl may be substituted with one, two or more (e.g., 1-5) R 1 'substitution'. R is R 1 ' may be the same or different and are independently selected from H, oxo, nitro, CN, C 1-15 Alkyl, C 1-15 An alkoxy group;
according to an embodiment of the invention, the R 1 Selected from unsubstituted or optionally substituted by one, two or more R 1 ' substitutedThe following groups:
wherein ,
represents a bond between a substituent and a benzene ring in the main structure; r is R 1a and R1b May be the same or different and are each independently selected from C 1-15 Alkyl, deuterated C 1-15 Alkyl or by one, two or more R d A substituted phenyl group; each R d Identical or different, independently of one another, from H, nitro, C 1-15 Alkyl, C 1-15 An alkoxy group; m may be selected from integers from 0 to 5; y is selected from C, O, S, C (O);
according to an embodiment of the invention, R 1 May be selected from unsubstituted or optionally substituted with one, two or more R 1 ' substituted following groups:
R 1a and R1b May be the same or different and are each independently selected from methyl, ethyl, propyl, isopropyl, butyl, deuterated methyl,
R d May be selected from H, nitro, ethoxy, ethyl, propyl, butyl, isopropyl, isobutyl; m may be 1 or 2; r is R 1 ' may be the same or different and are independently selected from H, nitro, ethoxy, ethyl, propyl, butyl, isopropyl, isobutyl.
As an example, the repeating unit of the polymer has the following structure:
wherein x and y have the definitions described above.
According to an embodiment of the invention, the number average molecular weight of the copolymer of formula (I) is 500-200000 daltons, such as 1000-100000 daltons, further such as 5000-50000 daltons.
The invention also provides a preparation method of the polymer, which comprises the following steps: a polymer having a repeating unit represented by the formula (II):
x、y、q、R 2 as defined above, the number of steps to be performed is,
reacting with sulfoxide compounds to obtain a polymer with a repeating unit shown as a formula (I);
optionally, the polymer with the repeating unit shown in the formula (I) is subjected to ion exchange with a corresponding anion solution to obtain polystyrene sulfonium salts with different anions.
The sulfoxide compound can be R 3 -SO-R 4 For example selected from:
wherein ,R1a 、R 1b 、R 3 、R 4 Y, m, x, y have the definition set out above;
according to an embodiment of the present invention, the reaction may be carried out under the action of a catalyst, which may be trifluoromethanesulfonic anhydride or trifluoromethanesulfonic acid;
according to an embodiment of the present invention, the molar ratio of polystyrene or its copolymer to sulfoxide compound in the reaction may be 1 (0.05 to 0.5), for example 1 (0.1 to 0.3).
According to the invention, polystyrene is reacted with R 3 -SO-R 4 Reacting to obtain a polymer with a repeating unit shown as a formula (I);
according to the invention, the polymer with the structure shown in the formula (II) is prepared by a method comprising the steps of polymerizing styrene and a compound shown in the formula (III) according to a certain proportion to obtain the polymer with the repeating unit shown in the formula (II),
x、y、q、R 2 as defined above.
The invention also provides application of the polymer as an acid generator in photoresist.
The invention also provides a photoresist composition comprising a polymer with a repeating unit shown in formula (I), a polymer with an acid sensitive functional group and a photoresist solvent.
According to an embodiment of the present invention, in the photoresist composition, the x value in the polymer is preferably greater than 0.1 and less than 0.3; the solubility of the main body material is obviously changed before and after exposure, and the performance of the photoresist is better.
According to embodiments of the present invention, the polymer of acid sensitive functional groups may be, for example, a copolymer of p-hydroxystyrene and p-hydroxystyrene protected by Boc groups, adamantyl methacrylate and butyrolactone methacrylate copolymer; for example, the following structure:
According to an embodiment of the present invention, the content of the repeating unit in the photoresist composition is 0.1% -5% of the total mass of the photoresist, and the balance is the polymer having an acid-sensitive functional group and the photoresist solvent.
According to an embodiment of the invention, the photoresist solvent is selected from one or more of the following: propylene glycol methyl ether acetate, cyclohexanone, ethyl n-pentanone, ethyl iso-pentanone, ethanol, acetonitrile, isopropanol, acetone.
A photoresist coating comprising the photoresist composition.
The invention also provides a preparation method of the photoresist coating, which comprises the step of forming a film on a substrate by spin coating the photoresist composition to obtain the chemically amplified photoresist coating.
In one embodiment, the substrate may be a silicon wafer or the like.
The invention also provides application of the photoresist coating in photoetching.
In one embodiment, the photoresist coating is used in modern lithography such as 365nm lithography, 248nm lithography, 193nm lithography, extreme ultraviolet lithography, nanoimprint lithography, or electron beam lithography; is especially suitable for 193nm, electron beam lithography, extreme Ultraviolet (EUV) and other high resolution lithography technologies.
Advantageous effects
The invention provides a styrene sulfonium salt polymer shown in a formula (I), which has simple synthesis process and cheap and easily obtained raw materials; the synthesized styrene sulfonium salt polymer is used as an acid generator in photoresist, so that the problems of poor solubility and uneven distribution of the acid generator in the chemically amplified photoresist are avoided, and the obtained pattern has very high resolution and low line width roughness. The styrene sulfonium salt polymer has long absorption wavelength by changing the structure of the sulfonium salt, so that the styrene sulfonium salt polymer can be used for deep ultraviolet lithography and ultraviolet lithography (365 nm).
Drawings
FIG. 1 is a scanning electron micrograph of Compound (1) in example 2 of the present invention.
FIG. 2 is a graph showing the thermal weight loss of the compound (1) in example 2 of the present invention.
FIG. 3 is a UV exposure pattern of a photoresist formulation containing compound (1) in example 6 of the present invention.
FIG. 4 is a graph showing a comparison of electron beam exposure patterns of a photoresist formulation (left) containing compound (1) and a photoresist formulation (right) containing a small molecule acid generator in example 7 of the present invention.
Definition and description of terms
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the claimed subject matter belongs.
"more" means three or more.
The term "halogen" includes F, cl, br or I.
The term "C 1-15 Alkyl "is understood to mean a straight-chain or branched saturated monovalent hydrocarbon radical having from 1 to 15 carbon atoms. For example, "C 1-6 Alkyl "means straight and branched alkyl groups having 1,2, 3, 4, 5, or 6 carbon atoms. The alkyl group is, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, 2-methylbutyl, 1-ethylpropyl, 1, 2-dimethylpropyl, neopentyl, 1-dimethylpropyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 2-ethylbutyl, 1-ethylbutyl, 3-dimethylbutyl, 2-dimethylbutyl, 1-dimethylbutyl, 2, 3-dimethylbutyl, 1, 3-dimethylbutyl, or 1, 2-dimethylbutyl, or the like, or an isomer thereof.
The term "C 1-15 Alkoxy "is understood to mean-O-C 1-15 Alkyl, wherein C 1-15 Alkyl has the above definition.
The term "aryl" is understood to mean an aromatic monocyclic, bicyclic or tricyclic hydrocarbon ring having 6 to 20 carbon atoms, preferably "C 6-14 Aryl group). For example, phenyl, naphthyl, fluorenyl, anthracyl, and the like.
Detailed Description
The technical scheme of the invention will be further described in detail below with reference to specific embodiments. It is to be understood that the following examples are illustrative only and are not to be construed as limiting the scope of the invention. All techniques implemented based on the above description of the invention are intended to be included within the scope of the invention.
Unless otherwise indicated, the starting materials and reagents used in the following examples were either commercially available or may be prepared by known methods.
Example 1.
Polystyrene was prepared and the synthetic route was as follows:
the method comprises the following specific steps: in a 500ml three-necked flask, styrene (100 ml), AIBN (2 g) and THF (200 ml) were added. Bubbling for 30min. The reaction was carried out at 70℃for 24h, and the reaction droplets were poured into methanol to precipitate. The resulting product was dried in vacuo. The weight average molecular weight was measured using GPC to be about 2000 daltons. Styrene of different molecular weights can also be prepared by other polymerization processes or purchased directly.
Example 2.
The polymer (1) was prepared as follows:
the method comprises the following specific steps: polystyrene prepared in example 1 was added to a 500ml Schlenk flask, followed by solvent DCM (200 ml) and DMSO (0.3 eq). Under the condition of-40 ℃ and under the condition of inert gas, trifluoro methanesulfonic anhydride (0.6 eq) is added dropwise. Stirring at room temperature overnight, dissolving the product with dichloromethane, dripping into n-hexane for precipitation to obtain the final product, wherein x is 0.25, y is 0.75, and vacuum drying. 1 H NMR(400MHz,DMSO)δ(ppm)7.67(s,2H),6.81(s,2H),3.16(s,1.5H),0.9-1.8(s,3H)。
Example 3.
Polymer (2) was prepared as follows:
the method comprises the following specific steps: polystyrene prepared in example 1 was added to a 500ml Schlenk flask, followed by solvent DCM (200 ml) and diphenyl sulfoxide (0.3 eq). Under the condition of-40 ℃ and under the condition of inert gas, trifluoro methanesulfonic anhydride (0.6 eq) is added dropwise. Stirring at room temperature overnight, dissolving the product with dichloromethane, and drippingPrecipitating with n-hexane to give final product with x of 0.17 and y of 0.83, and vacuum drying. 1 H NMR(400MHz,DMSO)δ(ppm)6.7-7.8(m,6.5H),0.9-1.8(s,3H)。
Example 4
The polymer (1) in example 2 was dissolved in acetonitrile to prepare a 30mg/ml solution, which was filtered with a microporous filter having a pore size of 0.22. Mu.m, to obtain a spin-coating solution, which was spin-coated on a silicon substrate to prepare a film, and the uniformity of the film was analyzed by scanning electron microscope SEM, as shown in FIG. 1, and the obtained film was very uniform.
Example 5
The thermal stability of the polymer (1) prepared in example 2 was measured, and the results showed that the decomposition temperatures thereof all reached 200℃or higher, and that the thermal stability was excellent, as shown in FIG. 2.
Example 6
Photoresist formulation and uv lithography: polymer (1) of example 2 and acid-sensitive polymer GBLMA-MAMA (repeating unit shown in the following figure, weight average molecular weight about 12000 daltons) were dissolved in PGMEA to prepare a solution with a mass concentration of 5%, and the solution was filtered with a microporous filter with a pore diameter of 0.22 μm to obtain a spin-coating solution, spin-coating a film on a silicon substrate, baking at 100℃for 3 minutes, and the prepared film was subjected to an exposure experiment (254 nm), developed with TMAH alkali solution to obtain very clear stripes with a line width of 1 μm, see FIG. 3. The resulting streak line edge roughness is very small.
Example 7
Photoresist formulation and electron beam lithography: polymer (1) of example 2 and acid-sensitive polymer GBLMA-MAMA (weight average molecular weight about 12000 daltons) were dissolved in PGMEA, filtered with a microporous filter having a pore size of 0.22 μm to obtain spin-coating liquid, spin-coated on a silicon substrate to prepare a film, and baked at 100deg.C for 3 minutes, and the prepared film was subjected to electron beam exposure to obtain a very clear 50nm stripe pattern with very small line edge roughness, as shown in FIG. 4 (left). And the resulting 50nm stripe pattern, with large line edge roughness, using commercial triphenylsulfonium salt as the acid generator, is shown in fig. 4 (right).
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A sulfonium salt polymer of styrene, the repeating unit of which has the structure of formula (I):
wherein: x and y represent the content percentages of the two monomers in the polymer, x+y=1, 0 < x < 0.3;
R 1 selected from sulfonium salt groups; r is R 1 The position of (c) may be para, meta or ortho; r is R 2 Selected from H, OH, halogen (Cl, F, I), C 1-15 Alkyl, C 1-15 Alkoxy, aryl; q is selected from integers from 1 to 5, preferably from 1 to 3;
X – is an anion, for example selected from the group consisting of halide, alkyl sulfonate, haloalkylsulfonate (e.g., triflate, perfluoropropyl sulfonate, perfluorobutyl sulfonate), p-toluenesulfonate, tetrafluoroborate, hexafluorophosphate, bis-trifluoromethanesulfonyl imide.
2. The polymer of claim 1, wherein R is 1 is-S + R 3 R 4, wherein ,R3 、R 4 Identical or different, independently selected from C 1-15 Alkyl, deuterated C 1-15 Alkyl, aryl, or R 3 、R 4 And S attached thereto form a 5-8 membered sulfur-containing heterocyclic group, optionally further containing 1-2 oxygen or sulfur, optionally with one or two benzeneRing fusion; the alkyl, aryl, sulfur-containing heterocyclic groups may be substituted with one, two or more R 1 ' substitution; each R 1 ' may be the same or different and are independently selected from H, nitro, CN, C 1-15 Alkyl, C 1-15 An alkoxy group.
3. The polymer according to claim 1 or 2, wherein R 1 Selected from unsubstituted or optionally substituted by one, two or more R 1 ' substituted following groups:
wherein ,
represents a bond between a substituent and a benzene ring in the main structure; r is R 1a and R1b May be the same or different and are each independently selected from C 1-15 Alkyl, deuterated C 1-15 Alkyl or by one, two or more R d A substituted phenyl group; each R d Identical or different, independently of one another, from H, nitro, C 1-15 Alkyl, C 1-15 An alkoxy group; m may be selected from integers from 0 to 5; y is selected from C, O, S, C (O). />
4. A polymer according to any one of claims 1 to 3, wherein R 1 Selected from unsubstituted or optionally substituted by one, two or more R 1 ' substituted following groups:
R 1a and R1b May be the same or different and are each independently selected from methyl, ethyl, propyl, isopropyl, butyl, deuterated methyl,
R d May be selected from H, nitro, ethoxy, ethyl, propyl, butyl, isopropyl, isobutyl; m may be 1 or 2; r is R 1 ' may be the same or different and are independently selected from H, nitro, ethoxy, ethyl, propyl, butyl, isopropyl, isobutyl.
5. The polymer of any one of claims 1-4, wherein the repeating units of the polymer are selected from the structures:
wherein x and y have the definition as defined in any one of claims 1 to 4.
6. A process for the preparation of a polymer as claimed in any one of claims 1 to 5, comprising the steps of: a polymer having a repeating unit represented by the formula (II):
x、y、q、R 2 as defined in any one of claims 1 to 5;
reacting with sulfoxide compounds to obtain a polymer with a repeating unit shown as a formula (I);
the sulfoxide compound can be R 3 -SO-R 4 For example selected from:
wherein ,R3 、R 4 、R 1a 、R 1b Y, m, x, y having the definition of any one of claims 1 to 5;
preferably, the reaction may be carried out over a catalyst which is trifluoromethanesulfonic anhydride or trifluoromethanesulfonic acid.
7. Use of a polymer according to any one of claims 1 to 5 as an acid generator in a photoresist.
8. A photoresist composition comprising the polymer of any one of claims 1-5, a polymer having acid sensitive functional groups, and a photoresist solvent;
preferably, in the photoresist composition, the x value in the polymer is greater than 0.1 and less than 0.3;
polymers of acid sensitive functional groups such as p-hydroxystyrene and Boc group protected p-hydroxystyrene copolymers, adamantyl methacrylate and butyrolactone methacrylate copolymers;
preferably, the content of the repeating unit in the photoresist composition is 0.1% -5% of the total mass of the photoresist, and the balance is the polymer with acid sensitive functional groups and the photoresist solvent.
Preferably, the photoresist solvent is selected from one or more of the following: propylene glycol methyl ether acetate, cyclohexanone, ethyl n-pentanone, ethyl iso-pentanone, ethanol, acetonitrile, isopropanol, acetone.
9. A photoresist coating comprising the photoresist composition of claim 8.
10. Use of the photoresist composition of claim 8 and/or the photoresist coating of claim 9 in lithography;
preferably, the photoresist coating is used in 365nm lithography, 248nm lithography, 193nm lithography, extreme ultraviolet lithography, nanoimprint lithography or electron beam lithography.
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| CN117700586A (en) * | 2024-02-05 | 2024-03-15 | 中国科学院理化技术研究所 | Polystyrene iodonium salt-based photoresist composition |
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| CN117700586A (en) * | 2024-02-05 | 2024-03-15 | 中国科学院理化技术研究所 | Polystyrene iodonium salt-based photoresist composition |
| CN117700586B (en) * | 2024-02-05 | 2024-05-28 | 中国科学院理化技术研究所 | Polystyrene iodonium salt-based photoresist composition |
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