CN116540493A - KrF photoresist and preparation method and patterning method thereof - Google Patents
KrF photoresist and preparation method and patterning method thereof Download PDFInfo
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- CN116540493A CN116540493A CN202310568802.1A CN202310568802A CN116540493A CN 116540493 A CN116540493 A CN 116540493A CN 202310568802 A CN202310568802 A CN 202310568802A CN 116540493 A CN116540493 A CN 116540493A
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- Prior art keywords
- photoacid
- monomer
- hyperbranched
- photoresist
- krf
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- 229920002120 photoresistant polymer Polymers 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims abstract description 9
- 238000000059 patterning Methods 0.000 title claims abstract description 7
- 239000000178 monomer Substances 0.000 claims abstract description 57
- 239000002952 polymeric resin Substances 0.000 claims abstract description 33
- 229920003002 synthetic resin Polymers 0.000 claims abstract description 33
- PYDFRCSZLSGAOG-UHFFFAOYSA-N 1-(4-ethenylphenyl)-1-phenylethanol Chemical compound CC(O)(c1ccccc1)c1ccc(C=C)cc1 PYDFRCSZLSGAOG-UHFFFAOYSA-N 0.000 claims abstract description 29
- FUGYGGDSWSUORM-UHFFFAOYSA-N 4-hydroxystyrene Chemical compound OC1=CC=C(C=C)C=C1 FUGYGGDSWSUORM-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 13
- 229920005989 resin Polymers 0.000 claims abstract description 13
- 239000011347 resin Substances 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 6
- 238000010791 quenching Methods 0.000 claims abstract description 6
- 230000000171 quenching effect Effects 0.000 claims abstract description 6
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 6
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical group CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000010559 graft polymerization reaction Methods 0.000 claims abstract 2
- 239000012790 adhesive layer Substances 0.000 claims description 22
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 20
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- MLLLIDBFMWYDQL-UHFFFAOYSA-N 2-ethenylbenzenesulfonyl chloride Chemical compound ClS(=O)(=O)C1=CC=CC=C1C=C MLLLIDBFMWYDQL-UHFFFAOYSA-N 0.000 claims description 7
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 239000003921 oil Substances 0.000 claims description 6
- 238000004528 spin coating Methods 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 6
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 5
- 238000012986 modification Methods 0.000 claims description 5
- 230000004048 modification Effects 0.000 claims description 5
- WHQSYGRFZMUQGQ-UHFFFAOYSA-N n,n-dimethylformamide;hydrate Chemical compound O.CN(C)C=O WHQSYGRFZMUQGQ-UHFFFAOYSA-N 0.000 claims description 5
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000005520 diaryliodonium group Chemical group 0.000 claims description 4
- 239000010410 layer Substances 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 125000005409 triarylsulfonium group Chemical group 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- COYBSBIBDYUILE-UHFFFAOYSA-N 2-[bis(2-hydroxyethyl)amino]ethyl acetate Chemical compound CC(=O)OCCN(CCO)CCO COYBSBIBDYUILE-UHFFFAOYSA-N 0.000 claims description 3
- CFMZSMGAMPBRBE-UHFFFAOYSA-N 2-hydroxyisoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(O)C(=O)C2=C1 CFMZSMGAMPBRBE-UHFFFAOYSA-N 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 239000011159 matrix material Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- VRLOMVGLFOVCKX-UHFFFAOYSA-N n-ethoxy-2-methoxyethanamine Chemical compound CCONCCOC VRLOMVGLFOVCKX-UHFFFAOYSA-N 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- XESUCHPMWXMNRV-UHFFFAOYSA-M sodium;2-ethenylbenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1C=C XESUCHPMWXMNRV-UHFFFAOYSA-M 0.000 claims description 3
- XFTALRAZSCGSKN-UHFFFAOYSA-M sodium;4-ethenylbenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=C(C=C)C=C1 XFTALRAZSCGSKN-UHFFFAOYSA-M 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000012955 diaryliodonium Substances 0.000 claims description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 2
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000013067 intermediate product Substances 0.000 claims description 2
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 claims description 2
- QHSPZGZEUDEIQM-UHFFFAOYSA-N tert-butyl but-2-enoate Chemical compound CC=CC(=O)OC(C)(C)C QHSPZGZEUDEIQM-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 abstract description 10
- 238000009792 diffusion process Methods 0.000 abstract description 5
- 239000000243 solution Substances 0.000 description 11
- 230000035945 sensitivity Effects 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 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 5
- 238000011161 development Methods 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- -1 PAG small molecules Chemical class 0.000 description 3
- 238000010511 deprotection reaction Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 238000001132 ultrasonic dispersion Methods 0.000 description 2
- JAMNSIXSLVPNLC-UHFFFAOYSA-N (4-ethenylphenyl) acetate Chemical compound CC(=O)OC1=CC=C(C=C)C=C1 JAMNSIXSLVPNLC-UHFFFAOYSA-N 0.000 description 1
- XLLXMBCBJGATSP-UHFFFAOYSA-N 2-phenylethenol Chemical compound OC=CC1=CC=CC=C1 XLLXMBCBJGATSP-UHFFFAOYSA-N 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- DJOWTWWHMWQATC-KYHIUUMWSA-N Karpoxanthin Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1(O)C(C)(C)CC(O)CC1(C)O)C=CC=C(/C)C=CC2=C(C)CC(O)CC2(C)C DJOWTWWHMWQATC-KYHIUUMWSA-N 0.000 description 1
- 238000010934 O-alkylation reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229960003328 benzoyl peroxide Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- JESXATFQYMPTNL-UHFFFAOYSA-N mono-hydroxyphenyl-ethylene Natural products OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000007847 structural defect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- ZFEAYIKULRXTAR-UHFFFAOYSA-M triphenylsulfanium;chloride Chemical compound [Cl-].C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 ZFEAYIKULRXTAR-UHFFFAOYSA-M 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/16—Coating processes; Apparatus therefor
- G03F7/162—Coating on a rotating support, e.g. using a whirler or a spinner
-
- 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
- G03F7/16—Coating processes; Apparatus therefor
- G03F7/168—Finishing the coated layer, e.g. drying, baking, soaking
Abstract
The invention provides a KrF photoresist, which is characterized in that: comprises 48.5 to 60.5 percent of hyperbranched photoacid polymeric resin, 0.5 to 1 percent of quenching agent, 0.03 to 0.5 percent of leveling agent and 50 to 72 percent of solvent by weight percent; the hyperbranched photoacid polymerization resin is prepared by hyperbranched polymerization of polyalcohol, p-hydroxystyrene monomer, alkenyl tertiary butyl ester, photoacid monomer and 4- (1-phenyl-1-hydroxyethyl) styrene; the 4- (1-phenyl-1-hydroxyethyl) styrene hyperbranched graft polymerization is carried out on the terminal base region of the polymerized p-hydroxystyrene monomer, alkenyl tert-butyl ester and photoacid monomer. Meanwhile, the invention also provides a preparation method of the KrF photoresist and a patterning method thereof. The chain structure of the invention can reduce the diffusion of protonic acid generated by the group of the easy photoacid to a non-exposure area, reduce the entanglement of molecular chains, improve the resolution ratio and the LER performance, and reduce the Tg value.
Description
Technical Field
The invention relates to the technical field of photoresist, in particular to a KrF photoresist, a preparation method thereof and a patterning method.
Background
Resolution, line Edge Roughness (LER) and photoresistThere is a balance between sensitivity, and the formula can be: resolution ratio 3 The main challenge of chemical amplification technology is to improve resolution and sensitivity while ensuring that LER is low in order to meet advanced lithography requirements. KrF photoresists are mainly composed of four components: polymer resin, photosensitizer, photosensitive base and solvent. The following problems of the existing photoresist and film forming resin need to be solved: 1) The volatilization and diffusion of PAG and photoacid lead to the reduction of photoresist resolution and the occurrence of T-top phenomenon of photoresist morphology; 2) The linear polymer has large molecular weight, molecular chain entanglement is easy to occur, the resolution of the photoresist is reduced, and the edge roughness LER is increased; 3) The volume of the polymer is far larger than that of PAG small molecules, and the problems of structural defects and uneven resolution are caused by chain entanglement and grain boundary effect.
The film-forming polymer resin of the photoresist has a linear structure, and the linear polymer prepared by free radical polymerization has a large and compact molecular structure, large molecular weight and wide molecular weight distribution, and different molecular weights can cause the resolution of the photoresist to be reduced due to different dissolution rates. If fewer acid sensitive groups are present in the molecular chain, the sensitivity of the photoresist may be reduced; molecular chain entanglement can lead to reduced photoresist resolution and LER performance.
Disclosure of Invention
In order to solve the technical problems in the prior art in photoresist exposure and development, the invention provides a KrF photoresist, a preparation method thereof and a patterning method thereof.
In a first aspect, the invention provides a KrF photoresist, comprising 48.5-60.5% of hyperbranched photoacid polymer resin, 0.5-1% of quencher, 0.03-0.5% of leveling agent and 50-72% of solvent by weight percent;
the hyperbranched photoacid polymeric resin comprises hyperbranched ionic photoacid polymeric resin and nonionic photoacid polymeric resin;
the hyperbranched photoacid polymerization resin is prepared by hyperbranched polymerization of polyalcohol, p-hydroxystyrene monomer, alkenyl tert-butyl ester and photoacid monomer;
further, the hyperbranched photoacid polymerization resin can be prepared by hyperbranched polymerization of a polyol, a hydroxystyrene monomer, alkenyl tertiary butyl ester, a photoacid monomer and 4- (1-phenyl-1-hydroxyethyl) styrene;
preferably, the 4- (1-phenyl-1-hydroxyethyl) styrene is hyperbranched polymerized after the formation of a polymer of p-hydroxystyrene monomer, alkenyl tert-butyl ester, photoacid monomer.
Preferably, the tert-butyl alkenyl is at least one of tert-butyl acrylate and tert-butyl butenoate.
Preferably, the photoacid monomers include ionic photoacid monomers and nonionic photoacid monomers, wherein the ionic photoacid monomers are at least one of triarylsulfonium monomers and diaryliodonium monomers, and the nonionic photoacid monomers are N-sulfonyl dicarboximide monomers (PIT).
Further, the end group of the hyperbranched photoacid polymeric resin is a mercapto group.
Preferably, the quenching agent is an organic amine, and is at least one of trioctylamine, diethylamine, triethylamine, di-n-propylamine and tri-2- (2-methoxy (ethoxy) ethylamine).
Preferably, the solvent is at least one of Propylene Glycol Methyl Ether Acetate (PGMEA) or Propylene Glycol Methyl Ether (PGME).
Preferably, the hyperbranched photoacid polymeric resin has a molecular weight of 7500-50000 and the KrF photoresist formed has a Tg value of 123.5-139.6 ℃.
In a second aspect, the present invention provides a method for preparing a KrF photoresist:
s100: preparation of photoacid monomers
(1) Preparation of nonionic photoacid monomers
Dissolving sodium vinylbenzenesulfonate in DMF water solution, dispersing by ultrasonic wave, dripping thionyl chloride solution to obtain intermediate product vinylbenzenesulfonyl chloride, dissolving the prepared vinylbenzenesulfonyl chloride in pyridine and acetonitrile, adding N-hydroxyphthalimide, and fully reacting to obtain nonionic photoacid monomer;
(2) Preparation of ionic photoacid monomers
Dissolving sodium p-vinylbenzene sulfonate in DMF water solution, dispersing by ultrasonic wave, dripping diaryliodonium salt or triarylsulfonium salt water solution, and fully reacting to obtain the ionic photoacid monomer.
S200: preparation of hyperbranched photoacid polymeric resins
Dissolving polyhydric alcohol and 2- [ bis (2-hydroxyethyl) amino ] ethyl acetate in a solvent acetone, performing ultrasonic dispersion, fully reacting, respectively adding 60% -70% of p-hydroxystyrene monomer, 25% -35% of alkenyl tertiary butyl ester and 5% -10% of nonionic photoacid monomer prepared in the step S100 or ionic photoacid monomer prepared in the step S200 according to the weight ratio, fully stirring uniformly, adding an initiator, performing oil bath, fully reacting, adding thioglycollic acid for grafting modification, and adding an organic solvent for dilution to prepare the hyperbranched photoacid polymer resin.
Further, another preparation method is provided, wherein after an initiator and an oil bath are added for full reaction, 4- (1-phenyl-1-hydroxyethyl) styrene dissolved in an acetone solution is added for oil bath, thioglycollic acid is added for grafting modification, and after full reaction, hyperbranched photoacid polymeric resin is prepared.
S300: preparation of KrF photoresists
And (3) dissolving the prepared hyperbranched photoacid polymer resin in Propylene Glycol Methyl Ether Acetate (PGMEA) or Propylene Glycol Methyl Ether (PGME) solvent according to the weight percentage, and fully mixing the quenching agent and the leveling agent to prepare the KrF photoresist.
In a third aspect, the present invention provides a KrF photoresist patterning method:
(1) Providing a silicon-based substrate, baking at a high temperature, spin-coating the prepared KrF photoresist, and pre-baking to form a first adhesive layer;
(2) Coating photoresist with linear poly-p-hydroxystyrene as a matrix by secondary spin coating, and performing secondary pre-baking to form a second adhesive layer, wherein the relative thickness of the first adhesive layer and the second adhesive layer can be horizontally adjusted according to the failure rate of unrercut;
(3) And exposing and post-baking by using a KrF excimer laser light source, and developing to form a pattern layer.
The beneficial effects obtained by the invention are as follows:
(1) Because the resolution of the photoresist is reduced and the T-top defect appears in the shape of the photoresist due to the volatilization and diffusion of PAG and photoacid, the invention establishes a chain structure through hyperbranched, and the 4- (1-phenyl-1-hydroxyethyl) styrene with phenyl is grafted and polymerized at the tail end of the chain, and the group of the photoacid is polymerized in the chain, thereby reducing the diffusion of the protonic acid generated by the group of the photoacid to a non-exposure area and improving the resolution by wrapping the group of the photoacid;
(2) Molecular chain entanglement is reduced by forming a resin structure with a chain structure, so that the resolution ratio and LER performance of the photoresist are improved;
(3) By forming a resin structure with a chain structure, molecular chain entanglement is reduced, and Tg value is lowered;
(4) The photoacid group is polymerized in the hyperbranched chain structure, so that the reaction efficiency of the protonic acid in the wrapped structure can be obviously improved, the exposure energy is reduced, and the sensitivity and contrast of the KrF photoresist are improved;
(5) In the hyperbranched photoacid polymeric resin, the alkenyl tert-butyl group is decomposed to form a carboxylic acid group, so that side reactions in t-BOC deprotection, namely O-alkylation and C-alkylation of tert-butyl cations and the resin in t-BOC deprotection can be inhibited.
(6) In the prior art, acetoxyl is hydrolyzed under the conditions of acid and alkali to generate phenolic hydroxyl, the content of the phenolic hydroxyl is enhanced by polymerizing p-acetoxyl styrene, so as to improve the sensitivity and the adhesive force of the photoresist, the film retention rate of the photoresist is regulated, and the side reaction in the deprotection of t-BOC is avoided.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a DSC test data chart of example 1;
FIG. 2 is a graph of sensitivity test data for an embodiment;
FIG. 3 is a graph of photoresist development unrecicut yield test data for an example.
Detailed Description
In order that the above objects, features and advantages of the invention will be more clearly understood, a further description of the invention will be rendered by reference to the appended drawings and examples. It should be noted that, in the case of no conflict, the embodiments of the present application and the features in the embodiments may be combined with each other.
The invention will be further described with reference to the drawings and the specific examples.
Example 1: the invention provides a preparation method of a KrF photoresist, which comprises the following steps:
s100: preparation of nonionic photoacid monomers
1mol of sodium vinylbenzenesulfonate and 300mL of DMF aqueous solution are added into a three-neck flask, ultrasonic dispersion is carried out, 50mL of thionyl chloride solution is slowly added dropwise, magnetic stirring is carried out for 30min for full reaction, cold water bath is kept stand for 12H, desiccant and diethyl ether are added, and filtration and evaporation are carried out to obtain vinylbenzenesulfonyl chloride.
Adding the prepared vinyl benzene sulfonyl chloride into a three-neck flask, dissolving the vinyl benzene sulfonyl chloride in pyridine 0.55mol and 300mL of acetonitrile, adding N-hydroxyphthalimide, reacting for 5-6H, standing for 30min, and drying to obtain the N-sulfonyl phthalimide monomer.
S200: preparation of ionic photoacid monomers
1mol of sodium p-vinylbenzenesulfonate is taken and dissolved in 300mL of DMF water solution, the solution is dispersed by ultrasonic waves for 30min, 1mol of triphenylsulfonium chloride water solution is slowly added dropwise, and the reaction is continued for 3 to 5H.
S300: preparation of hyperbranched photoacid polymeric resins
Dissolving 1mol of polyhydric alcohol (Ji Mao tetrol) and 4mol of 2- [ bis (2-hydroxyethyl) amino ] ethyl acetate in a three-neck flask, adding 350mL of solvent acetone, dispersing by ultrasonic waves, fully reacting for 1H, respectively adding 60% -70% of p-hydroxystyrene monomer, 25% -35% of alkenyl tert-butyl ester, 5% -10% of nonionic photoacid monomer prepared in the step S100 or the ionic photoacid monomer prepared in the step S200 according to the weight ratio, fully stirring uniformly, adding an initiator Azodiisobutyronitrile (AIBN), carrying out oil bath at 65-75 ℃, fully reacting for 12H, preparing viscous liquid, adding thioglycollic acid for graft modification, adding acetone for dilution, and drying to prepare the hyperbranched photoacid polymer resin (4- (1-phenyl-1-hydroxyethyl) styrene is not added).
Adding initiator Azobisisobutyronitrile (AIBN), oil-bath at 65-75 ℃, fully reacting for 10-12 hours, adding 4- (1-phenyl-1-hydroxyethyl) styrene dissolved in acetone solution, oil-bath at 65-75 ℃, adding thioglycollic acid for grafting modification, fully reacting for 2-3 hours, and obtaining the hyperbranched photoacid polymeric resin (4- (1-phenyl-1-hydroxyethyl) styrene is added).
S300: preparation of KrF photoresists
According to weight percentage, the prepared hyperbranched nonionic photoacid polymeric resin (4- (1-phenyl-1-hydroxyethyl) styrene is not added), hyperbranched ionic photoacid polymeric resin (4- (1-phenyl-1-hydroxyethyl) styrene is added), and hyperbranched ionic photoacid polymeric resin (4- (1-phenyl-1-hydroxyethyl) styrene is added) is dissolved in Propylene Glycol Methyl Ether Acetate (PGMEA) or Propylene Glycol Methyl Ether (PGME) solvent, and the tri-2- (2-methoxy (ethoxy) ethylamine) flatting agent KP341 is fully mixed to prepare the KrF photoresist.
Example 2: photoresist DSC testing
And (3) fully mixing the para-hydroxystyrene monomer, the alkenyl tertiary butyl ester and the photoacid generator with the same weight proportion, dissolving in a solvent, adding a leveling agent and an organic amine quencher, preparing the linear poly-para-hydroxystyrene-based photoresist of the control test group, and carrying out parallel test on the linear poly-para-hydroxystyrene-based photoresist and the four photoresists prepared in the example 1, and testing the corresponding glass transition temperature. As shown in fig. 1:
from top to bottom, there are control group (linear poly-p-hydroxystyrene-based photoresist), hyperbranched ionic photoacid polymeric resin (4- (1-phenyl-1-hydroxyethyl) styrene has been added), hyperbranched nonionic photoacid polymeric resin (4- (1-phenyl-1-hydroxyethyl) styrene has not been added), hyperbranched ionic photoacid polymeric resin (4- (1-phenyl-1-hydroxyethyl) styrene has not been added), respectively.
As can be seen from fig. 1: the hyperbranched chain structure formed by the 4 polymer resins prepared in example 1 has a lower glass transition temperature Tg than the linear structure, and the glass transition temperature is reduced by at least 27 ℃ by forming the hyperbranched chain structure, mainly because the chain structure reduces the entanglement of the polymer; meanwhile, the higher the branching degree is, the more active branching points are, and more monomers participate in branching reaction, so that the average molecular chain segment length of the polymer is shortened, the molecular weight is reduced, the internal free volume of the polymer is increased, and the Tg of the polymer is reduced.
Meanwhile, as can be seen from fig. 1: the addition of 4- (1-phenyl-1-hydroxyethyl) styrene at the tail end of the chain for hyperbranched polymerization increases steric hindrance, and the glass transition temperature Tg is relatively higher than that of a photoresist which is not added with 4- (1-phenyl-1-hydroxyethyl) styrene for hyperbranched polymerization.
Example 3: sensitivity and contrast test
Control groups (linear poly-p-hydroxystyrene based photoresist, PR 1) were set and in the experiment: hyperbranched ionic photoacid polymeric resins (4- (1-phenyl-1-hydroxyethyl) styrene, PR2, hyperbranched ionic photoacid polymeric resins (4- (1-phenyl-1-hydroxyethyl) styrene, PR 3), hyperbranched nonionic photoacid polymeric resins (4- (1-phenyl-1-hydroxyethyl) styrene, PR 4) and hyperbranched ionic photoacid polymeric resins (4- (1-phenyl-1-hydroxyethyl) styrene, PR 5) were added. The photoresist of the control group and the experimental group is spin-coated on a silicon substrate, and then the pattern layer is obtained through film coating, baking, exposure, baking, development and ion implantation.
As can be seen from FIG. 2, under the same light source condition and exposure time, the sensitivity of the 4 hyperbranched photoacid polymerization resins is better than that of the control group, wherein the exposure energy required by the resin which is not added with 4- (1-phenyl-1-hydroxyethyl) styrene for polymerization in the experimental group is smaller than that required by the resin which is added with 4- (1-phenyl-1-hydroxyethyl), because the thermal stability of tert-butyl ester mainly determines the required exposure energy, in the resin with the same mass fraction, PR4 and PR5 acrylic acid tert-butyl ester are added more, the acid generating capacity is stronger, and PR1 and PR2 are added with 4- (1-phenyl-1-hydroxyethyl) styrene for polymerization, and the 4- (1-phenyl-1-hydroxyethyl) styrene is hydrolyzed under protonic acid, so that the hydroxy is eliminated and converted into double bond, and the overall acid generating capacity is weaker.
Meanwhile, as can be seen from table 1, the contrast ratio of PR1 and PR2 is greater than that of PR4 and PR5, because 4- (1-phenyl-1-hydroxyethyl) styrene is polymerized at the tail of the chain segment, because the proton acid cannot have a crosslinking reaction with the resin of the non-exposed region due to steric hindrance of the benzene ring, the hydrolysis of the 4- (1-phenyl-1-hydroxyethyl) styrene at the tail of the chain is nearly catalyzed, the LER is reduced, and the contrast ratio is improved.
TABLE 1
Example 4: photoresist development unrercut yield test
Providing a silicon-based substrate, baking at a high temperature, spin-coating the KrF photoresist (PR 2 or PR 3) prepared in example 1, and pre-baking to form a first adhesive layer; coating photoresist with linear poly-p-hydroxystyrene as a matrix by secondary spin coating, and performing secondary pre-baking to form a second adhesive layer, wherein the relative thickness of the first adhesive layer and the second adhesive layer can be horizontally adjusted according to the failure rate of unrercut; and exposing and post-baking by using a KrF excimer laser light source, and developing to form a pattern layer.
And the relative thickness of the first adhesive layer and the second adhesive layer is from (0-2): 1, as shown in fig. 3, by adjusting the relative thicknesses of the first adhesive layer and the second adhesive layer, the unrecicut failure rate can be optimized, and the relative thicknesses of the first adhesive layer and the second adhesive layer are from (0.5-1): in the section of 1, the unrercut failure rate decreases. Because the substrate photoacid capability of the first adhesive layer is different from that of the second adhesive layer, the photoresist with strong photoacid capability is arranged at the bottom of the adhesive layer, and unrercut failure caused by insufficient exposure energy of the adhesive layer at the bottom or incomplete bonding and developing with the substrate can be obviously reduced.
The photoresist prepared in this example: 1) The defects of reduced resolution of the photoresist and occurrence of T-top of the photoresist morphology caused by volatilization and diffusion of PAG and photoacid can be reduced; 2) Meanwhile, molecular chain entanglement is reduced, so that resolution ratio and LER performance of the photoresist are improved, and Tg value is reduced; 3) By polymerizing the photoacid groups in the hyperbranched chain structure, the proton acid can obviously improve the reaction efficiency inside the wrapped structure, reduce the exposure energy and improve the sensitivity and contrast of the KrF photoresist.
The present invention can be easily implemented by those skilled in the art through the above specific embodiments. It should be understood that the invention is not limited to the particular embodiments described above. Based on the disclosed embodiments, a person skilled in the art can combine different technical features at will, so as to realize different technical schemes.
Claims (10)
1. A KrF photoresist characterized by: comprises 48.5 to 60.5 percent of hyperbranched photoacid polymeric resin, 0.5 to 1 percent of quenching agent, 0.03 to 0.5 percent of leveling agent and 50 to 72 percent of solvent by weight percent;
the hyperbranched photoacid polymerization resin is prepared by hyperbranched polymerization of polyalcohol, p-hydroxystyrene monomer, alkenyl tertiary butyl ester, photoacid monomer and 4- (1-phenyl-1-hydroxyethyl) styrene;
the 4- (1-phenyl-1-hydroxyethyl) styrene hyperbranched graft polymerization is carried out on the terminal base region of the polymerized p-hydroxystyrene monomer, alkenyl tert-butyl ester and photoacid monomer.
2. The KrF photoresist according to claim 1, wherein: the photoacid monomers include ionic photoacid monomers and nonionic photoacid monomers.
3. The KrF photoresist according to claim 2, wherein: the ionic photoacid monomer is at least one of triarylsulfonium monomer and diaryl iodonium monomer, and the nonionic photoacid monomer is N-sulfonyl dicarboximide monomer (PIT).
4. The KrF photoresist according to claim 1, wherein: the alkenyl tert-butyl ester is at least one of tert-butyl acrylate and tert-butyl butenoate.
5. The KrF photoresist according to claim 1, wherein: the quenching agent is organic amine, and is at least one of trioctylamine, diethylamine, triethylamine, di-n-propylamine and tri-2- (2-methoxy (ethoxy) ethylamine).
6. The KrF photoresist according to claim 1, wherein: the solvent is at least one of Propylene Glycol Methyl Ether Acetate (PGMEA) or Propylene Glycol Methyl Ether (PGME).
7. The KrF photoresist according to claim 1, wherein: the molecular weight of the hyperbranched photoacid polymer resin is 7500-50000, and the Tg value of the formed KrF photoresist is 123.5-139.6 ℃.
8. A preparation method of a KrF photoresist is characterized by comprising the following steps:
s100: preparation of photoacid monomers
(1) Preparation of nonionic photoacid monomers
Dissolving sodium vinylbenzenesulfonate in DMF water solution, dispersing by ultrasonic wave, dripping thionyl chloride solution to obtain intermediate product vinylbenzenesulfonyl chloride, dissolving the prepared vinylbenzenesulfonyl chloride in pyridine and acetonitrile, adding N-hydroxyphthalimide, and fully reacting to obtain the nonionic photoacid monomer;
(2) Preparation of ionic photoacid monomers
Dissolving sodium p-vinylbenzene sulfonate in DMF water solution, dispersing by ultrasonic wave, dripping diaryliodonium salt or triarylsulfonium salt water solution, and fully reacting to obtain the ionic photoacid monomer;
s200: preparation of hyperbranched photoacid polymeric resins
Dissolving polyalcohol and 2- [ bis (2-hydroxyethyl) amino ] ethyl acetate in a solvent acetone, dispersing by ultrasonic waves, fully reacting, respectively adding p-hydroxystyrene monomer, alkenyl tert-butyl ester, the nonionic photoacid monomer prepared in the step S100 or the ionic photoacid monomer prepared in the step S200 according to the weight ratio, fully and uniformly stirring, adding an initiator, an oil bath, fully reacting, adding acetone solution-dissolved 4- (1-phenyl-1-hydroxyethyl) styrene, an oil bath, adding thioglycollic acid for grafting modification, and fully reacting to obtain the hyperbranched photoacid polymer resin;
s300: preparation of KrF photoresists
And (3) dissolving the prepared hyperbranched photoacid polymer resin in Propylene Glycol Methyl Ether Acetate (PGMEA) or Propylene Glycol Methyl Ether (PGME) solvent according to the weight percentage, and fully mixing a quenching agent and a leveling agent to prepare the KrF photoresist.
9. The method for preparing the KrF photoresist according to claim 8, wherein: 60-70% of the p-hydroxystyrene monomer, 25-35% of the alkenyl tert-butyl ester, 5-10% of the nonionic photoacid monomer prepared in the step S100 or the ionic photoacid monomer prepared in the step S200 are added according to the weight percentage.
10. A KrF photoresist patterning method, characterized in that:
(1) Providing a silicon-based substrate, baking at a high temperature, spin-coating the prepared KrF photoresist, and pre-baking to form a first adhesive layer;
(2) Coating photoresist with linear poly-p-hydroxystyrene as a matrix by secondary spin coating, and performing secondary pre-baking to form a second adhesive layer, wherein the relative thickness of the first adhesive layer and the second adhesive layer can be adjusted according to the unrercut failure rate level;
(3) And exposing and post-baking by using a KrF excimer laser light source, and developing to form a pattern layer.
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