CN110554565A - Photosensitive polymer and preparation method and application thereof - Google Patents
Photosensitive polymer and preparation method and application thereof Download PDFInfo
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- CN110554565A CN110554565A CN201810558655.9A CN201810558655A CN110554565A CN 110554565 A CN110554565 A CN 110554565A CN 201810558655 A CN201810558655 A CN 201810558655A CN 110554565 A CN110554565 A CN 110554565A
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- 229920000642 polymer Polymers 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 229920005989 resin Polymers 0.000 claims abstract description 40
- 239000011347 resin Substances 0.000 claims abstract description 40
- 229920002120 photoresistant polymer Polymers 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims description 31
- 239000002904 solvent Substances 0.000 claims description 17
- 150000003839 salts Chemical group 0.000 claims description 13
- 125000004122 cyclic group Chemical group 0.000 claims description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 10
- 239000000758 substrate Substances 0.000 claims description 10
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 claims description 8
- GRWFGVWFFZKLTI-UHFFFAOYSA-N α-pinene Chemical compound CC1=CCC2C(C)(C)C1C2 GRWFGVWFFZKLTI-UHFFFAOYSA-N 0.000 claims description 8
- 230000009477 glass transition Effects 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 5
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical class I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 5
- GRWFGVWFFZKLTI-IUCAKERBSA-N 1S,5S-(-)-alpha-Pinene Natural products CC1=CC[C@@H]2C(C)(C)[C@H]1C2 GRWFGVWFFZKLTI-IUCAKERBSA-N 0.000 claims description 4
- MVNCAPSFBDBCGF-UHFFFAOYSA-N alpha-pinene Natural products CC1=CCC23C1CC2C3(C)C MVNCAPSFBDBCGF-UHFFFAOYSA-N 0.000 claims description 4
- 125000003700 epoxy group Chemical group 0.000 claims description 4
- 125000004185 ester group Chemical group 0.000 claims description 4
- 125000001033 ether group Chemical group 0.000 claims description 4
- 150000004714 phosphonium salts Chemical class 0.000 claims description 4
- 238000005903 acid hydrolysis reaction Methods 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 3
- OMBRFUXPXNIUCZ-UHFFFAOYSA-N dioxidonitrogen(1+) Chemical class O=[N+]=O OMBRFUXPXNIUCZ-UHFFFAOYSA-N 0.000 claims description 3
- 230000031700 light absorption Effects 0.000 claims description 2
- 239000011342 resin composition Substances 0.000 abstract description 21
- 238000007654 immersion Methods 0.000 abstract description 2
- 125000000217 alkyl group Chemical group 0.000 description 30
- 239000002253 acid Substances 0.000 description 22
- 229910052736 halogen Inorganic materials 0.000 description 18
- 125000001424 substituent group Chemical group 0.000 description 16
- 239000000178 monomer Substances 0.000 description 15
- 230000008569 process Effects 0.000 description 15
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 14
- 150000002367 halogens Chemical class 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- -1 e.g. Chemical class 0.000 description 12
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 12
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 12
- 238000001259 photo etching Methods 0.000 description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 8
- 229910052731 fluorine Inorganic materials 0.000 description 8
- 239000011737 fluorine Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 238000006467 substitution reaction Methods 0.000 description 8
- 238000009826 distribution Methods 0.000 description 7
- 229940116333 ethyl lactate Drugs 0.000 description 7
- 125000005843 halogen group Chemical group 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 7
- 238000000206 photolithography Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- 235000019400 benzoyl peroxide Nutrition 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000001459 lithography Methods 0.000 description 5
- 125000006736 (C6-C20) aryl group Chemical group 0.000 description 4
- 125000000041 C6-C10 aryl group Chemical group 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- 125000006165 cyclic alkyl group Chemical group 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000002861 polymer material Substances 0.000 description 4
- 239000002952 polymeric resin Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 238000004528 spin coating Methods 0.000 description 4
- 238000001308 synthesis method Methods 0.000 description 4
- 229920003002 synthetic resin Polymers 0.000 description 4
- 229910021642 ultra pure water Inorganic materials 0.000 description 4
- 239000012498 ultrapure water Substances 0.000 description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000000671 immersion lithography Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 3
- 150000003384 small molecules Chemical class 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 125000002243 cyclohexanonyl group Chemical group *C1(*)C(=O)C(*)(*)C(*)(*)C(*)(*)C1(*)* 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexyloxide Natural products O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000006552 photochemical reaction Methods 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 125000000027 (C1-C10) alkoxy group Chemical group 0.000 description 1
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000005615 azonium group Chemical group 0.000 description 1
- BLBKTJIPOBRUGU-UHFFFAOYSA-M benzenesulfonate;triphenylsulfanium Chemical compound [O-]S(=O)(=O)C1=CC=CC=C1.C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 BLBKTJIPOBRUGU-UHFFFAOYSA-M 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 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
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- YFSUTJLHUFNCNZ-UHFFFAOYSA-N perfluorooctane-1-sulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YFSUTJLHUFNCNZ-UHFFFAOYSA-N 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 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
- JLUOZBQVJZLHPN-UHFFFAOYSA-N tert-butyl(phenyl)iodanium Chemical class CC(C)(C)[I+]C1=CC=CC=C1 JLUOZBQVJZLHPN-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000003809 water extraction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
-
- 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
-
- 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
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/42—Stripping or agents therefor
- G03F7/422—Stripping or agents therefor using liquids only
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Materials For Photolithography (AREA)
Abstract
the invention relates to a photosensitive polymer and a preparation method and application thereof. The invention discloses a photosensitive polymer, a photosensitive resin composition containing the photosensitive polymer, and application of the photosensitive resin in a chemically amplified photoresist, in particular an immersion photoresist.
Description
Technical Field
The invention belongs to the field of photoresponse materials, and particularly relates to a photosensitive polymer material, a photosensitive resin composition containing the photosensitive polymer material, a hardened film prepared from the photosensitive resin composition, a preparation method of the hardened film, and various integrated circuit elements containing the hardened film.
background
Integrated Circuits (ICs) are one of the most critical technologies in the information age, and all devices related to electronic operations cannot be separated from chips from daily life to industrial production, and just because of the chips with increasingly powerful functions, personal computers have become capable of integrating increasingly powerful functions, and mobile phones have been able to enter 3G and 4G ages. In the fabrication of integrated circuits, photolithography (photolithography) is a key technology that holds great importance. The functions of the chip can be continuously improved without departing from the development of photoetching technology materials and processes.
Photolithography is a process of transferring a predetermined pattern on a mask onto a substrate using a photochemical reaction. In the photolithography process, photoresist (photo-resist) is the most critical material. Incident light passes through the mask plate, so that patterns on the mask plate are projected onto photoresist coated on a substrate, photochemical reaction is excited, baking and development are carried out, and photoresist patterns are formed and then serve as blocking layers for selectively blocking subsequent etching or ion implantation and the like.
photoresists are designed for the exposure wavelength and typically contain a polymeric resin (resin), a Photo Acid Generator (PAG), and solvents and additives as the major components. Currently, the photoresist used for 248nm and 193nm in the international market occupies a huge market space, and the photoresist used in the international market is generally chemical-amplified resist (chemically-amplified resist). The main components of a chemically amplified glue are generally a resin, a photoacid generator and corresponding solvents and additives. In which an acid labile group (acid labilefunctional group) is generally attached to the molecular chain of the polymer resin, which makes the polymer insoluble in a developer. The photosensitive acid generator is a photosensitive compound, which decomposes under light to generate acids (H +), and these acids can act as a catalyst to cause the acid labile groups on the molecular chain of the polymer resin to be detached and new acids to be generated during post-exposure bake (PEB) process. The polarity of the polymer resin changes with the shedding of the acid labile group, and the photoresist becomes soluble in a developer.
From the transition from contact exposure to projection exposure in the 80 s lithography, the exposure wavelength of the photoresist technology was shifted from broad-spectrum ultraviolet to the direction of G-line (436nm) → I-line (365nm) → KrF (248nm) → ArF (193nm) → EUV (13.5 nm). Since 2003, the semiconductor industry has entered the 90nm lithography process era using ArF lasers, which is currently the mainstream lithography technology internationally and will continue to extend. According to a resolution calculation formula: r (resolution) ═ k (process constant) NA (light flux)/lambda (wavelength), semiconductor processes below 90nm all depend on 193nm photoresist, 193nm photoetching can be divided into 193nm dry photoetching and 193nm wet photoetching according to the difference of media between a wafer and a lens in an exposure system, wherein air is arranged between the wafer and the lens of the 193nm dry photoetching, the light flux (NA) is less than 1.0, and the 193nm dry photoetching can only meet the resolution of the semiconductor processes of 90nm and 65 nm; in the semiconductor process with the resolution of less than 45nm, water is used to replace air to obtain a high-resolution photoetching process with the light transmission amount of 1.07-1.35 NA, so 193nm wet photoresist is needed in the semiconductor process for manufacturing higher-end semiconductors such as 45nm, 32nm, 22nm, 14nm and 10 nm. Higher imaging resolution means finer lithographic process dimensions, and also higher performance, lower power consumption, and higher chip integration and lower cost. Correspondingly, 193nm immersion lithography also places some special requirements on the photoresist: leaching of small molecules of the photoresist material in water must be limited or the leached small molecules may cause contamination of the lens of the lithography machine.
The photosensitive acid generators commonly used in photoresists are primarily onium salts, such as iodonium salts, e.g., tert-butyl phenyl iodonium salt perfluorooctane sulfonic acid; or as a sulfonium salt, such as triphenylsulfonium salt benzenesulfonic acid, the photosensitive acid generator is typically dissolved in a solvent with the resin to form a homogeneous liquid for spin-coating. After spin coating, the solvent is volatilized by a baking process, so that the photoresist material can be uniformly distributed on the surface of the substrate.
At present, photosensitive acid generators in photoresist are generally used to be dissolved in a solvent together with resin to form a uniform liquid, and then the uniform liquid is used as photoresist for subsequent application. One problem is that the photoacid generator molecules are difficult to achieve uniformity in the solution system. Photosensitive acid generators tend to approach the same molecule in this system and even self-aggregate and form molecular groups. Once the distribution of the photo acid generator is non-uniform, the distribution of the amount of acid generated by light exposure is also non-uniform, which is detrimental to the lithographic image achieving a higher contrast (dt/dD, where t is the thickness of the resist after development and D is the intensity of the exposure), resulting in a rough lithographic pattern.
Therefore, there is still a need in the art to develop a photosensitive polymer material that is less prone to self-aggregation, so that the distribution of the photosensitive acid generator is more uniform, thereby improving the quality of the image obtained by photolithography, and at the same time, the leaching of small molecules of the photoresist in the water immersion environment of 193nm immersion lithography is as little as possible or not.
disclosure of Invention
The invention aims to provide a high-sensitivity polymer for a chemically amplified photoresist, which can efficiently generate acid under the irradiation of ultraviolet light with the wavelength ranging from 150nm to 260 nm.
The invention also aims to provide a photosensitive resin composition containing the photosensitive polymer and a preparation method thereof.
The invention also aims to provide a hardened film made of the photosensitive resin composition and a preparation method thereof.
The first aspect of the present invention provides a photosensitive polymer comprising the following structural units:
(a1) The method comprises the following steps A structural unit having a carboxyl group or other acidic group generated by acid hydrolysis;
(a2) The method comprises the following steps A structural unit having an onium salt group;
(a3) the method comprises the following steps A structural unit having a cyclic group;
Wherein the molar ratio of the structural unit (a2) is 1 to 80% and the molar ratio of the structural unit (a3) is 20 to 99% based on all the structural units constituting the photosensitive polymer.
In another preferred embodiment, the photosensitive polymer is a high photosensitive polymer for a chemically amplified photoresist capable of efficiently producing acid under the irradiation of ultraviolet light with the wavelength ranging from 150nm to 260nm, and the polymer has no significant absorption at the use wavelength.
in another preferred embodiment, the ion precipitation amount of the photoresist prepared from the photosensitive polymer in the exposure medium water in the 193immersion type exposure process meets the ASML standard, and meanwhile, no outgas occurs, so that the lens pollution is avoided, and higher resolution can be obtained.
In another preferred embodiment, the structural unit (a1) has a hydrolyzable group selected from an ester group, an ether group and/or an epoxy group.
In another preferred embodiment, the structural unit (a1) is one or more of the following formulae:
In the general formulae (1A), (1B) and (1C), Ra 1, Ra 2, Ra 1 ', Ra 2', Ra 1 ", Ra 2" and Ra 3 "represent substituents;
Wherein Ra 1, Ra 1 ', Ra 1' can be selected from the group consisting of non-, fully-, or partially-halogenated C1-C10 linear alkyl groups, fully-or partially-halogenated C1-C10 branched alkyl groups, substituted or unsubstituted C6-C20 cyclic alkyl groups;
Ra 2, Ra 2', Ra 2 "and Ra 3" can be selected from the group consisting of substituted or unsubstituted C1-C30 straight or branched alkyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C3-C30 cyclic alkyl, substituted or unsubstituted C6-C30 aryl;
Wherein, one or more hydrogen atoms of the substituent refers to a group substituted by one or more substituents selected from the group consisting of: oxo (═ O), halogen (preferably fluorine), hydroxy, carboxy, C1-C6 straight or branched alkyl unsubstituted or substituted with hydroxy or halogen, C6-C10 aryl unsubstituted or substituted with hydroxy or halogen.
In another preferred embodiment, the structural unit (a2) is a structural unit having an onium salt group; wherein the onium salt group is selected from the group consisting of: an iodonium salt, a sulfonium salt, a phosphonium salt, a nitronium salt, or a combination thereof.
In another preferred embodiment, the structural unit (a2) is one or more of the following formulae:
In the general formulae (2A), (2B), (2C) and (2D),
A - can be selected from sulfonate, nitrate;
Rb 1, Rb 2, Rb 3, Rb 1 ', Rb 2 ', Rb 3 ', Rb 4 ', Rb 1 ", Rb 2", Rb 3 ", Rb 4", Rb 5 ", Rb 1" ', Rb 2 "', Rb 3" ', Rb 4 "' and Rb 5" ' represent substituents;
Wherein,
Rb 1, Rb 1 ', Rb 1 "and Rb 1'" can comprise one or more of a fully or partially halogenated C1-C10 straight chain alkyl group, a fully or partially halogenated C1-C10 branched alkyl group, a substituted or unsubstituted C3-C30 cyclic alkyl group, a substituted or unsubstituted C6-C20 aryl group;
rb 2, Rb 3, Rb 2 ', Rb 3 ', Rb 4 ', Rb 2 ', Rb 3 ', Rb 4 ', Rb 5 ', Rb 2 ', Rb 3 ', Rb 4 ' and Rb 5 ' can be substituted or unsubstituted C1-C12 straight-chain or branched alkyl or substituted or unsubstituted C6-C20 aryl;
Wherein said substitution means substitution with one or more substituents selected from the group consisting of one or more hydrogen atoms of the group: halogen (preferably fluorine), hydroxy, carboxy, linear or branched C1-C6 alkyl unsubstituted or substituted by hydroxy or halogen, C6-C10 aryl unsubstituted or substituted by hydroxy or halogen.
In another preferred embodiment, the structural unit (a3) is a structural unit having a cyclic group, wherein the cyclic group is selected from the group consisting of: adamantane, styrene, alpha-pinene, or combinations thereof.
In another preferred embodiment, the structural unit (a3) is one or more of the following formulae:
In the general formulae (3A), (3B) and (3C),
rc 1, Rc 1', and Rc 1 ″ may have one or more of the following structures, non-substituted or unsubstituted C1-C10 straight-chain alkyl group, substituted or unsubstituted C1-C10 branched alkyl group, substituted or unsubstituted C3-C30 cyclic alkyl group, wherein said substitution means that one or more hydrogen atoms of the group are substituted by one or more substituents selected from the group consisting of halogen (preferably fluorine), hydroxyl, carboxyl;
rc 2, Rc 2' and Rc 2 "represent substituents, which may be selected from one or more of hydrogen, halogen, substituted or unsubstituted C1-C30 straight or branched alkyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C6-C30 aryl, wherein said substitution means that one or more hydrogen atoms of the group are substituted by one or more substituents selected from the group consisting of halogen (preferably fluorine), hydroxy, carboxy.
in another preferred embodiment, the photosensitive polymer satisfies one or more of the following properties:
1) The polydispersity PDI is less than or equal to 1.80;
2) The molecular weight is 2000-200000;
3) The glass transition temperature Tg is 60-240 ℃;
4) The light absorption is weak or none in the range of 180-240 nm.
The second aspect of the present invention provides a photosensitive resin comprising the following components: (A) a photosensitive polymer according to the first aspect of the present invention; and (B) a solvent.
in another preferred example, the solvent is cyclohexanone, Ethyl Lactate (EL), Propylene Glycol Methyl Ether Acetate (PGMEA), or Propylene Glycol Methyl Ether (PGME).
In another preferred embodiment, the concentration of the component A is 1 to 10 wt%.
The third aspect of the present invention provides a use of the photosensitive resin of the second aspect for producing a cured film.
In another preferred embodiment, the photoresist is formed by curing the photosensitive resin according to the second aspect of the present invention.
The fourth aspect of the present invention provides a method for producing a hardened film, the method comprising the steps of:
1) Applying a photosensitive resin according to the second aspect of the present invention to a substrate;
2) Baking the coated photosensitive resin for the first time to remove the solvent;
3) Exposing the photosensitive resin after the solvent is removed;
4) Carrying out secondary baking on the exposed photosensitive resin;
5) The photosensitive resin after the secondary baking is developed with a developer to obtain a cured film.
in another preferred embodiment, the coating is by spin coating.
In another preferred example, the substrate is a silicon plate.
in another preferred embodiment, the substrate is coated with hexamethyldisilazane before the photosensitive resin according to the second aspect is coated.
In another preferred embodiment, the primary baking is performed at 90 ℃ for 120 seconds.
In another preferred embodiment, the exposure is performed using a 193 photo-etching machine.
In another preferred embodiment, the secondary baking is performed at 120 ℃ for 60 seconds.
In another preferred example, the developer is an alkaline aqueous developer.
In another preferred embodiment, the developing solution is an aqueous solution of tetramethylammonium hydroxide.
in another preferred embodiment, the development is carried out for 60s to 120 s.
In another preferred embodiment, the resulting polymer film is rinsed with ultrapure water.
The fifth aspect of the present invention provides a photoresist prepared from the photosensitive polymer according to the first aspect of the present invention or the photosensitive resin according to the second aspect of the present invention; or by the production method described in the fourth aspect.
It is to be understood that within the scope of the present invention, the above-described features of the present invention and those specifically described below (e.g., in the examples) may be combined with each other to form new or preferred embodiments. Not to be reiterated herein, but to the extent of space.
Drawings
FIG. 1 is a GPC measurement curve of the polymer P1 obtained in example 1.
FIG. 2 is a DSC of polymer P1.
FIG. 3 is a CD-SEM measurement of a lithographic pattern obtained using a photosensitive resin composition containing Polymer P1.
FIG. 4 is a GPC measurement curve of the polymer P1 obtained in example 4.
FIG. 5 is a DSC of polymer P2.
FIG. 6 is a CD-SEM measurement of a lithographic pattern obtained using a photosensitive resin composition containing Polymer P2.
Detailed Description
The present inventors have made extensive and intensive studies and as a result, have surprisingly found for the first time that a monomer which is useful as a photoacid generator can be copolymerized with other monomers to give a polymer material having a group which is useful as a photoacid generator suspended in the main chain. Because the photoacid generator groups are fixed on the main chain, the difficulty of mutual gathering and even self-aggregation of the photoacid generator groups is greatly improved, the distribution uniformity of the photoacid generator is improved, and the image quality obtained by photoetching is improved. And the photoresist prepared from the photosensitive polymer prepared by the invention is not easy to separate out ions in water, thereby avoiding the pollution to a lens in an immersion lithography process and improving the resolution of an image. The present invention has been completed based on this finding.
term(s) for
As used herein, "straight chain alkyl" refers to an alkyl group without branching.
As used herein, "branched alkyl" refers to an alkyl group having a branch.
As used herein, "C1-C10 straight chain alkyl" refers to straight chain alkyl groups having 1-10 carbon atoms, such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, and the like.
as used herein, "C1-C10 branched alkyl" refers to an alkyl group having a branch of 1-10 carbon atoms, such as isopropyl, isobutyl, tert-butyl, isopentyl, and the like.
other similar names have similar definitions, such as "C1-C30 straight or branched alkyl" and the like.
as used herein, "C3-C30 cyclic alkyl" refers to cyclic alkyl groups having 3-30 carbon atoms, e.g., cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like. Other similar names have similar definitions, such as "C3-C10 cyclic alkyl" and the like.
As used herein, "C1-C10 alkoxy" refers to a straight or branched chain alkyl-O-group having 1-10 carbon atoms.
As used herein, "C6-C30 aryl" refers to aryl groups having 6-30 carbon atoms, such as phenyl, naphthyl, phenanthryl, anthracyl, and the like. Other similar names have similar definitions, such as "C6-C10 cyclic alkyl" and the like.
As used herein, "perhalo" refers to a group in which all of the hydrogen atoms are replaced with halogen atoms.
As used herein, "partially halogenated" means that the hydrogen atom portion of the group is replaced with a halogen atom.
As used herein, "halo" refers to fluoro, chloro, iodo, or bromo.
photosensitive polymer
The invention provides a photosensitive polymer. The photosensitive polymer is a high photosensitive polymer for chemically amplified photoresist, which can efficiently generate acid under the irradiation of ultraviolet light with the wavelength of 150nm-260 nm. The photosensitive polymer does not absorb significantly at the wavelength of use. And the ion precipitation of the photoresist prepared from the photosensitive polymer under 193im polymerization meets the ASML standard, cannot cause lens pollution, and can obtain higher resolution.
the photosensitive polymer satisfies one or more of the following properties:
1) The polydispersity PDI is less than or equal to 1.80;
2) The molecular weight is 2000-200000;
3) the glass transition temperature Tg is 60-240 ℃;
4) the light is weak to no absorption within the range of 180-240 nm.
the photosensitive polymer of the present invention comprises the following structural units:
(a1) The method comprises the following steps A structural unit having a carboxyl group or other acidic group generated by acid hydrolysis;
(a2) the method comprises the following steps A structural unit having an onium salt group;
(a3) the method comprises the following steps A structural unit having a cyclic group;
wherein the molar ratio of the structural unit (a2) is 1 to 80% and the molar ratio of the structural unit (a3) is 20 to 99% based on all the structural units constituting the photosensitive polymer.
Constitutional unit (a1)
the structural unit (a1) has a hydrolyzable group selected from an ester group, an ether group and/or an epoxy group.
the structural unit (a1) is one or more of the following formulae:
In the general formulae (1A), (1B) and (1C), Ra 1, Ra 2, Ra 1 ', Ra 2 ', Ra 1 ', Ra 2 ' and Ra 3 ' represent substituents,
Ra 1, Ra 1 ', Ra 1' can be selected from the group consisting of non-, fully-, or partially-halogenated C1-C10 linear alkyl groups, fully-or partially-halogenated C1-C10 branched alkyl groups, substituted or unsubstituted C6-C20 cyclic alkyl groups;
Ra 2, Ra 2', Ra 2 "and Ra 3" can be selected from the group consisting of substituted or unsubstituted C1-C30 straight or branched alkyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C3-C30 cyclic alkyl, substituted or unsubstituted C6-C30 aryl;
Wherein, one or more hydrogen atoms of the substituent refers to a group substituted by one or more substituents selected from the group consisting of: oxo (═ O), halogen (preferably fluorine), hydroxy, carboxy, C1-C6 straight or branched alkyl unsubstituted or substituted with hydroxy or halogen, C6-C10 aryl unsubstituted or substituted with hydroxy or halogen.
Constitutional unit (a2)
the structural unit (a2) is a structural unit having an onium salt group; wherein the onium salt group is selected from the group consisting of: an iodonium salt, a sulfonium salt, a phosphonium salt, a nitronium salt, or a combination thereof.
The structural unit (a2) is one or more of the following formulae:
In the general formulae (2A), (2B), (2C) and (2D),
A - can be selected from sulfonate, nitrate;
rb 1, Rb 2, Rb 3, Rb 1 ', Rb 2 ', Rb 3 ', Rb 4 ', Rb 1 ", Rb 2", Rb 3 ", Rb 4", Rb 5 ", Rb 1" ', Rb 2 "', Rb 3" ', Rb 4 "' and Rb 5" ' represent substituents,
Rb 1, Rb 1 ', Rb 1 "and Rb 1'" can comprise one or more of a fully or partially halogenated C1-C10 straight chain alkyl group, a fully or partially halogenated C1-C10 branched alkyl group, a substituted or unsubstituted C3-C30 cyclic alkyl group, a substituted or unsubstituted C6-C20 aryl group;
Rb 2, Rb 3, Rb 2 ', Rb 3 ', Rb 4 ', Rb 2 ', Rb 3 ', Rb 4 ', Rb 5 ', Rb 2 ', Rb 3 ', Rb 4 ' and Rb 5 ' can be substituted or unsubstituted chain or branched C1-C12 straight chain or branched alkyl or substituted or unsubstituted C6-C20 aryl;
Wherein said substitution means substitution with one or more substituents selected from the group consisting of one or more hydrogen atoms of the group: halogen (preferably fluorine), hydroxy, carboxy, C1-C6 straight or branched alkyl unsubstituted or substituted with hydroxy or halogen, C6-C10 aryl unsubstituted or substituted with hydroxy or halogen.
constitutional unit (a3)
The structural unit (a3) is a structural unit having a cyclic group, wherein the cyclic group is selected from the group consisting of: adamantane, styrene, alpha-pinene, or combinations thereof.
the structural unit (a3) is one or more of the following formulae:
In the general formulae (3A), (3B) and (3C),
Rc 1, Rc 1', and Rc 1 ″ may have one or more structures selected from the group consisting of a non-substituted or unsubstituted C1-C10 linear alkyl group, a substituted or unsubstituted C1-C10 branched alkyl group, a substituted or unsubstituted C3-C30 alicyclic hydrocarbon group, wherein the substitution means that one or more hydrogen atoms of the group are substituted with one or more substituents selected from the group consisting of halogen (preferably fluorine), hydroxyl, carboxyl;
Rc 2, Rc 2' and Rc 2 "represent substituents, which may be selected from one or more of hydrogen, halogen, substituted or unsubstituted C1-C30 straight or branched alkyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C6-C30 aryl, wherein said substitution means that one or more hydrogen atoms of the group are substituted by one or more substituents selected from the group consisting of halogen (preferably fluorine), hydroxy, carboxy.
method for preparing photosensitive polymer
the preparation method of the photosensitive polymer comprises the following steps:
1) dissolving one or more monomers selected from the following group in an organic solvent for reaction:
(b1) a monomer having a hydrolyzable group selected from an ester group, an ether group and/or an epoxy group;
(b2) A monomer having an onium salt group; wherein the onium salt group is selected from the group consisting of: an iodonium salt, a sulfonium salt, a phosphonium salt, a azonium salt, or a combination thereof;
(b3) A monomer having a cyclic group, wherein the cyclic group is selected from the group consisting of: adamantane, styrene, alpha-pinene, or combinations thereof;
The reaction temperature is controlled between 25 ℃ and 200 ℃; preferably 50 to 150 ℃;
The reaction time length is controlled to be 10min-72h (preferably 40min-48h, more preferably 1h-24 h);
in the step 1), an initiator dibenzoyl peroxide is added into the reaction mixture before the reaction.
2) Then adding a quenching agent to terminate the reaction;
3) Removing the solvent in the reaction system to obtain residual precipitate;
4) the obtained precipitate was dried by heating in an oven.
the molar ratio of the monomer having an onium salt group (b2) is 1 to 80% and the molar ratio of the monomer having a cyclic group (b3) is 20 to 99% with respect to all monomers.
photosensitive resin
the invention provides a photosensitive resin, which contains the following components: (A) a photosensitive polymer according to the present invention; and (B) a solvent.
the solvent is cyclohexanone, ethyl lactate, propylene glycol methyl ether acetate or propylene glycol methyl ether.
the concentration of the component A is 1-10 wt%.
hardened film
The invention provides a cured film prepared from the photosensitive polymer or the photosensitive resin of the invention.
Specifically, the preparation method can be prepared by the following preparation method, and the method comprises the following steps:
1) Coating the photosensitive resin on a substrate;
2) baking the coated photosensitive resin for the first time to remove the solvent;
3) Exposing the photosensitive resin after the solvent is removed;
4) Carrying out secondary baking on the exposed photosensitive resin;
5) the photosensitive resin after the secondary baking is developed with a developer to obtain a cured film.
In another preferred embodiment, the coating is by spin coating.
In another preferred example, the substrate is a silicon plate.
In another preferred embodiment, the substrate is coated with hexamethyldisilazane before the photosensitive resin of the present invention is coated.
in another preferred embodiment, the primary baking is performed at 90 ℃ for 120 seconds.
In another preferred embodiment, the exposure is performed using a 193 photo-etching machine.
In another preferred embodiment, the secondary baking is performed at 120 ℃ for 60 seconds.
in another preferred example, the developer is an alkaline aqueous developer.
in another preferred embodiment, the developing solution is an aqueous solution of tetramethylammonium hydroxide.
In another preferred example, the development is performed for 60 seconds.
in another preferred embodiment, the obtained cured film is rinsed with ultrapure water.
universal test method
gel Permeation Chromatograph (GPC)
in the present invention, the number average molecular weight (Mn) and the polydispersity PDI can be measured by gel chromatography (tetrahydrofuran phase), corrected using a general calibration method, and based on styrene as a calibration standard.
Scanning electron microscope for microspur measurement (CD-SEM)
In the present invention, the size of the image obtained by exposure can be measured by a macro-scanning electron microscope.
differential Scanning Calorimeter (DSC)
the glass transition temperature (Tg) of a photosensitive polymeric material is measured using differential scanning calorimetry Q2000 (DSC). The temperature rise program is that the temperature rises to 10 ℃ per minute from minus 60 ℃ to 160 ℃, then the temperature is reduced to minus 60 ℃ at the same speed and is recorded as a first cycle, the main function is to eliminate the heat history of the sample, and the temperature rise program of a second cycle is still that the temperature rises to twenty ℃ per minute from minus 60 ℃ to 160 ℃. The DSC images of the present application are all the results of the second cycle measurements.
(water-extraction-and-analysis apparatus,WEXA)&
(LC)
the method adopts a water extraction analyzer (WEXA) to sample deionized water contacted with the photoresist, and utilizes a Liquid Chromatograph (LC) to analyze the ion precipitation content in a water sample.
The main advantages of the invention include:
1. In the photosensitive resin, because the photosensitive acid generator groups are fixed on the main chain, the difficulty of mutual gathering and even self-aggregation of the photosensitive acid generator groups is greatly improved, and the distribution uniformity of the photosensitive acid generator is improved, so that the quality of a photoetching image prepared by using the photosensitive resin is improved.
2. The photosensitive resin prepared by the photosensitive polymer can be used for 193immersion lithography, and the concentration of ions precipitated by the material in water meets the ASML standard, so that the pollution to a lens can not be caused.
3. The image obtained when the photosensitive resin prepared by the photosensitive polymer is exposed on the ASML1100 has narrow line width range and low line width roughness.
In conclusion, the photosensitive resin prepared by the photosensitive polymer of the present invention can be applied to 193 photoresist and can obtain good resolution.
the invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out under conventional conditions or conditions recommended by the manufacturers. Unless otherwise indicated, percentages and parts are percentages and parts by weight.
The test materials and reagents used in the following examples are commercially available without specific reference.
Example 1: synthesis method of photosensitive polymer
Dissolving 16.5g of monomer M1, 12g of monomer M2 and 15g of monomer M3 with 60mL of acetonitrile, transferring the solution into a reaction bottle, increasing the temperature of a mixed solution system to 90 ℃, adding 0.15g of dibenzoyl peroxide (BPO), uniformly mixing, increasing the temperature of the reaction system to 100 ℃, continuing to react for 8h, adding 5mL of ethanol to terminate the reaction, precipitating the mixed solution after the reaction is terminated in the ethanol, and heating and drying the obtained solid in an oven at 100 ℃ for 8h to obtain white powdery polymer P138.5g.
The structural formulas of M1, M2 and M3 are as follows:
the number average molecular weight of polymer P1 was 21320, and the molecular weight distribution (PDI) was 1.30, as determined by Gel Permeation Chromatography (GPC). As shown in fig. 1.
FIG. 2 is a DSC of polymer P1. As shown, the glass transition temperature is 125.21 ℃.
example 2: a synthesis method of a photosensitive resin composition comprises the following steps:
25g of the polymer P1 described in example 1 was taken, and the polymer was dissolved in Ethyl Lactate (EL) until the polymer concentration became about 5% by mass, and the solution was filtered through a polytetrafluoroethylene filter having a bore diameter of 0.2. mu.m, to obtain a photosensitive resin composition.
Example 3: a method for processing and using a photosensitive resin composition comprises the following steps:
Hexamethyldisilazane (HDMS) was spin-coated on a 12-inch silicon plate, and then the photosensitive resin composition of example 2 was spin-coated on the above-mentioned hexamethyldisilazane film, and a photosensitive resin composition film layer having a thickness of 75 to 80nm was obtained by baking at 90 ℃/120 s.
After obtaining the photosensitive resin composition film layer, the photosensitive resin composition film layer was exposed to an L/S pattern using a 193 photo-lithography machine (PAS 5500/1100B manufactured by ArF eximer scanner, ASML).
After the exposure, post-exposure baking (PEB) was performed at 120 ℃/60s on a hot stage, and the exposed resist film layer was developed for 60s with an alkaline aqueous developer (2.38 mass% tetramethylammonium hydroxide aqueous solution (TMAH aqueous solution)), and then rinsed with ultrapure water to obtain a resist pattern.
the resulting pattern was measured using a CD-SEM, including image size, image Line Width Roughness (LWR).
as a result of the test, when the photoresist is used for 193immersion type exposure, the concentration of ions precipitated in water meets ASML standards, the pollution of a lens cannot be caused, the exposure is carried out on ASML1100, an image with the line width range of 100-105nm is obtained, and the LWR is 9.3nm and is less than 10%. The results are shown in FIG. 3. The photosensitive resin of the present invention can be applied to 193 photoresist and can obtain higher resolution.
Example 4: synthesis method of photosensitive polymer
Dissolving 18g of monomer M4, 14.5g of monomer M5 and 16g of monomer M6 by using 60mL of acetonitrile, transferring the solution into a reaction bottle, increasing the temperature of a mixed solution system to 90 ℃, adding 0.165g of dibenzoyl peroxide (BPO), uniformly mixing, increasing the temperature of the reaction system to 100 ℃, continuing to react for 8h, adding 5mL of ethanol to terminate the reaction, precipitating the mixed solution after terminating the reaction in ethanol, and heating and drying the obtained solid in an oven at 100 ℃ for 8h to obtain white powdery polymer P240.2g.
The structural formulas of M4, M5 and M6 are as follows:
polymer P1 was found to have a number average molecular weight of 22400 and a molecular weight distribution (PDI) of 1.27 by Gel Permeation Chromatography (GPC). As shown in fig. 4.
FIG. 5 is a DSC of polymer P2. As shown, the glass transition temperature is 132.86 ℃.
Example 5: a synthesis method of a photosensitive resin composition comprises the following steps:
25g of the polymer P2 described in example 1 was taken, and the polymer was dissolved in Ethyl Lactate (EL) until the polymer concentration became about 10% by mass, and the solution was filtered through a polytetrafluoroethylene filter having a bore diameter of 0.2. mu.m, to obtain a photosensitive resin composition.
Example 6: a method for processing and using a photosensitive resin composition comprises the following steps:
Hexamethyldisilazane (HDMS) was spin-coated on a 12-inch silicon plate, and then the photosensitive resin composition of example 2 was spin-coated on the above-mentioned hexamethyldisilazane film, and a photosensitive resin composition film layer having a thickness of 75 to 80nm was obtained by baking at 90 ℃/120 s.
after obtaining the photosensitive resin composition film layer, the photosensitive resin composition film layer was exposed to an L/S pattern using a 193 photo-lithography machine (PAS 5500/1100B manufactured by ArF eximer scanner, ASML).
after the exposure, post-exposure baking (PEB) was performed at 120 ℃/60s on a hot stage, and the exposed resist film layer was developed for 60s with an alkaline aqueous developer (2.38 mass% tetramethylammonium hydroxide aqueous solution (TMAH aqueous solution)), and then rinsed with ultrapure water to obtain a resist pattern.
The resulting pattern was measured using a CD-SEM, including image size, image Line Width Roughness (LWR).
test results show that when the photoresist is used for 193immersion type exposure, the concentration of ions precipitated in water meets ASML standards, the pollution of a lens cannot be caused, exposure is carried out on ASML1100, an image with the line width of 98nm is obtained, and the LWR is 9.1nm and is less than 10%. The results are shown in FIG. 6. The photosensitive resin of the present invention can be applied to 193 photoresist and can obtain higher resolution.
all documents referred to herein are incorporated by reference into this application as if each were individually incorporated by reference. Furthermore, it should be understood that various changes and modifications of the present invention can be made by those skilled in the art after reading the above teachings of the present invention, and these equivalents also fall within the scope of the present invention as defined by the appended claims.
Claims (10)
1. A photosensitive polymer comprising the following structural unit:
(a1) the method comprises the following steps A structural unit having a carboxyl group or other acidic group generated by acid hydrolysis;
(a2) The method comprises the following steps A structural unit having an onium salt group;
(a3) The method comprises the following steps A structural unit having a cyclic group;
Wherein the molar ratio of the structural unit (a2) is 1 to 80% and the molar ratio of the structural unit (a3) is 20 to 99% based on all the structural units constituting the photosensitive polymer.
2. The photosensitive polymer according to claim 1, wherein the structural unit (a1) has a hydrolyzable group selected from an ester group, an ether group and/or an epoxy group.
3. The photosensitive polymer according to claim 1, wherein the structural unit (a2) is a structural unit having an onium salt group; wherein the onium salt group is selected from the group consisting of: an iodonium salt, a sulfonium salt, a phosphonium salt, a nitronium salt, or a combination thereof.
4. The photosensitive polymer according to claim 1, wherein the structural unit (a3) is a structural unit having a cyclic group, wherein the cyclic group is selected from the group consisting of: adamantane, styrene, alpha-pinene, or combinations thereof.
5. A photosensitive polymer according to any one of claims 1 to 4, wherein the photosensitive polymer satisfies one or more of the following properties:
1) The polydispersity PDI is less than or equal to 1.80;
2) The molecular weight is 2000-200000;
3) The glass transition temperature Tg is 60-240 ℃;
4) The light absorption is weak or none in the range of 180-240 nm.
6. a photosensitive resin, characterized by comprising the following components: (A) a photosensitive polymer as described in any one of claims 1 to 5; and (B) a solvent.
7. The photosensitive resin according to claim 6, wherein the concentration of the component A is 1 to 10 wt%.
8. use of the photosensitive resin according to claim 6 for producing a cured film.
9. A method for producing a hardened film, characterized by comprising the steps of:
1) Applying the photosensitive resin of claim 6 to a substrate;
2) Baking the coated photosensitive resin for the first time to remove the solvent;
3) exposing the photosensitive resin after the solvent is removed;
4) Carrying out secondary baking on the exposed photosensitive resin;
5) The photosensitive resin after the secondary baking is developed with a developer to obtain a cured film.
10. A photoresist prepared from the photosensitive polymer of claim 1 or the photosensitive resin of claim 6; or by the production method according to claim 9.
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| US20220252981A1 (en) * | 2021-01-29 | 2022-08-11 | Canton Litho Material Technology Inc. | Highly sequenced copolymer for dual-tone photoresists, resist composition and patterning process thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008133448A (en) * | 2006-10-27 | 2008-06-12 | Shin Etsu Chem Co Ltd | Sulfonium salt having polymerizable anion and polymer compound, resist material and method for pattern formation |
| US20090269696A1 (en) * | 2008-04-24 | 2009-10-29 | Youichi Ohsawa | Sulfonium salt-containing polymer, resist composition, and patterning process |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008133448A (en) * | 2006-10-27 | 2008-06-12 | Shin Etsu Chem Co Ltd | Sulfonium salt having polymerizable anion and polymer compound, resist material and method for pattern formation |
| US20090269696A1 (en) * | 2008-04-24 | 2009-10-29 | Youichi Ohsawa | Sulfonium salt-containing polymer, resist composition, and patterning process |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US20220252981A1 (en) * | 2021-01-29 | 2022-08-11 | Canton Litho Material Technology Inc. | Highly sequenced copolymer for dual-tone photoresists, resist composition and patterning process thereof |
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