CN109679020B - Cubane-containing acrylate film-forming resin and ArF photoresist as well as preparation method and photoetching method thereof - Google Patents
Cubane-containing acrylate film-forming resin and ArF photoresist as well as preparation method and photoetching method thereof Download PDFInfo
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- CN109679020B CN109679020B CN201811620801.2A CN201811620801A CN109679020B CN 109679020 B CN109679020 B CN 109679020B CN 201811620801 A CN201811620801 A CN 201811620801A CN 109679020 B CN109679020 B CN 109679020B
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- acrylate
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- 229920002120 photoresistant polymer Polymers 0.000 title claims abstract description 69
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title claims abstract description 53
- 239000011347 resin Substances 0.000 title claims abstract description 47
- 229920005989 resin Polymers 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 44
- TXWRERCHRDBNLG-UHFFFAOYSA-N cubane Chemical compound C12C3C4C1C1C4C3C12 TXWRERCHRDBNLG-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000001259 photo etching Methods 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 239000000178 monomer Substances 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 3
- -1 t-butoxycarbonyl Chemical group 0.000 claims description 25
- 239000002904 solvent Substances 0.000 claims description 18
- 239000000758 substrate Substances 0.000 claims description 18
- 239000000654 additive Substances 0.000 claims description 15
- 230000000996 additive effect Effects 0.000 claims description 11
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 6
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 6
- 238000009826 distribution Methods 0.000 claims description 5
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- XLLIQLLCWZCATF-UHFFFAOYSA-N ethylene glycol monomethyl ether acetate Natural products COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical compound C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 claims description 2
- YUBKBLFRGDNIDR-UHFFFAOYSA-N 2-ethyladamantan-2-ol Chemical compound C1C(C2)CC3CC1C(CC)(O)C2C3 YUBKBLFRGDNIDR-UHFFFAOYSA-N 0.000 claims description 2
- JKOZWMQUOWYZAB-UHFFFAOYSA-N 2-methyladamantan-2-ol Chemical compound C1C(C2)CC3CC1C(C)(O)C2C3 JKOZWMQUOWYZAB-UHFFFAOYSA-N 0.000 claims description 2
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 claims description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 2
- DTGKSKDOIYIVQL-MRTMQBJTSA-N Isoborneol Natural products C1C[C@@]2(C)[C@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-MRTMQBJTSA-N 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- CKDOCTFBFTVPSN-UHFFFAOYSA-N borneol Natural products C1CC2(C)C(C)CC1C2(C)C CKDOCTFBFTVPSN-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 2
- XCIXKGXIYUWCLL-UHFFFAOYSA-N cyclopentanol Chemical compound OC1CCCC1 XCIXKGXIYUWCLL-UHFFFAOYSA-N 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- DTGKSKDOIYIVQL-UHFFFAOYSA-N dl-isoborneol Natural products C1CC2(C)C(O)CC1C2(C)C DTGKSKDOIYIVQL-UHFFFAOYSA-N 0.000 claims description 2
- 239000003623 enhancer Substances 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000003292 glue Substances 0.000 claims description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical group I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 2
- 150000002896 organic halogen compounds Chemical class 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000003504 photosensitizing agent Substances 0.000 claims description 2
- 239000004014 plasticizer Substances 0.000 claims description 2
- 238000004528 spin coating Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 229920001897 terpolymer Polymers 0.000 claims 1
- 229920006029 tetra-polymer Polymers 0.000 claims 1
- 238000005530 etching Methods 0.000 abstract description 21
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 239000004065 semiconductor Substances 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000004033 plastic Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 229910003481 amorphous carbon Inorganic materials 0.000 description 7
- 238000000206 photolithography Methods 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 7
- 239000010703 silicon Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- FDYDISGSYGFRJM-UHFFFAOYSA-N (2-methyl-2-adamantyl) 2-methylprop-2-enoate Chemical compound C1C(C2)CC3CC1C(OC(=O)C(=C)C)(C)C2C3 FDYDISGSYGFRJM-UHFFFAOYSA-N 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 3
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 230000003667 anti-reflective effect Effects 0.000 description 3
- YCZWJBIXAUQULS-UHFFFAOYSA-M bis(4-methylphenyl)iodanium;bromide Chemical compound [Br-].C1=CC(C)=CC=C1[I+]C1=CC=C(C)C=C1 YCZWJBIXAUQULS-UHFFFAOYSA-M 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000004205 dimethyl polysiloxane Substances 0.000 description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 239000007870 radical polymerization initiator Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- AWRJQAGOUMAUGW-UHFFFAOYSA-N [4-(hydroxymethyl)cuban-1-yl]methanol Chemical compound C12C3C4(CO)C1C1C4C3C12CO AWRJQAGOUMAUGW-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 235000012431 wafers Nutrition 0.000 description 2
- DCTVCFJTKSQXED-UHFFFAOYSA-N (2-ethyl-2-adamantyl) 2-methylprop-2-enoate Chemical compound C1C(C2)CC3CC1C(CC)(OC(=O)C(C)=C)C2C3 DCTVCFJTKSQXED-UHFFFAOYSA-N 0.000 description 1
- GMOMPFWGNASTIA-UHFFFAOYSA-N 2,3,4-tribromocyclopentan-1-one Chemical compound BrC1C(CC(C1Br)Br)=O GMOMPFWGNASTIA-UHFFFAOYSA-N 0.000 description 1
- SSZQFFQYQDZGNX-UHFFFAOYSA-N 2-bromocyclopenta-2,4-dien-1-one Chemical compound BrC1=CC=CC1=O SSZQFFQYQDZGNX-UHFFFAOYSA-N 0.000 description 1
- BZKFMUIJRXWWQK-UHFFFAOYSA-N Cyclopentenone Chemical compound O=C1CCC=C1 BZKFMUIJRXWWQK-UHFFFAOYSA-N 0.000 description 1
- 238000007162 Favorskii rearrangement reaction Methods 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- IAXXETNIOYFMLW-GYSYKLTISA-N [(1r,3r,4r)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical group C1C[C@@]2(C)[C@H](OC(=O)C(=C)C)C[C@@H]1C2(C)C IAXXETNIOYFMLW-GYSYKLTISA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000006352 cycloaddition reaction Methods 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- CEIPQQODRKXDSB-UHFFFAOYSA-N ethyl 3-(6-hydroxynaphthalen-2-yl)-1H-indazole-5-carboximidate dihydrochloride Chemical compound Cl.Cl.C1=C(O)C=CC2=CC(C3=NNC4=CC=C(C=C43)C(=N)OCC)=CC=C21 CEIPQQODRKXDSB-UHFFFAOYSA-N 0.000 description 1
- 238000006142 intramolecular cycloaddition reaction Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229920006027 ternary co-polymer Polymers 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
- C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
-
- 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
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- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (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 belongs to the field of semiconductors and integrated circuits, and particularly discloses an acrylate film-forming resin containing cubane, an ArF photoresist, a preparation method of the acrylate film-forming resin and the ArF photoresist and a photoetching method of the acrylate film-forming resin. The ArF photoresist contains a film-forming resin and a photoacid generator, wherein the film-forming resin is obtained by copolymerizing 20-60 mass percent of unit monomer I with a structure shown in a formula (1) and 40-80 mass percent of unit monomer II with a structure shown in a formula (2), and R is1And R1Each independently being a hydrogen atom or a methyl group, R2Is an acid labile group. The photoresist provided by the invention has better etching resistance, a hard mask layer is not required to be adopted in the photoetching process, and a new photoetching process is adopted to replace the hard mask process, so that the hard mask layer can be omitted, and the etching resistance equivalent to or even better than that of the original process can be achieved. In addition, the photoetching process provided by the invention only needs a rotary spin coater for subsequent photoetching, and does not need a CVD machine, thereby achieving the purposes of reducing material cost and production time.
Description
Technical Field
The invention belongs to the field of semiconductors and integrated circuits, and particularly relates to cubane-containing acrylate film-forming resin and an ArF photoresist as well as a preparation method and a photoetching method thereof.
Background
ArF photoresist is used in photolithography processes for semiconductor and integrated circuit fabrication when the Critical Dimension (CD) is less than 90 nm. Generally, between ArF photoresist and substrate, it is required to use amorphous carbon compound (a-carbon) and silicon oxynitride (SiON) as hard mask layers to improve etching resistance, and to match ArF anti-reflection layers to improve resolution. As shown in a in fig. 1, firstly, an amorphous carbon layer (a-carbon), a silicon oxynitride layer (SiON), an anti-reflection layer (BARC) and a patterned ArF photoresist layer (ArF PR) are sequentially formed on a substrate (substrate); etching the anti-reflection layer by taking the patterned ArF photoresist layer as a mask to form a patterned anti-reflection layer, and removing the patterned ArF photoresist layer; etching the silicon oxynitride layer by taking the patterned anti-reflection layer as a mask to form a patterned silicon oxynitride layer, and removing the patterned anti-reflection layer; etching the amorphous carbon layer by taking the patterned silicon oxynitride layer as a mask to form a patterned amorphous carbon layer, and removing the patterned silicon oxynitride layer; and etching the substrate by taking the patterned amorphous carbon layer as a mask to form a patterned substrate, and removing the patterned amorphous carbon layer. Therefore, the ArF photoresist with excellent etching resistance is developed, a hard mask layer is not needed in the photoetching process, the process route is shortened, and the purposes of reducing material cost and production time are achieved.
Disclosure of Invention
The invention aims to provide cubane-containing acrylate film-forming resin with excellent etching resistance, an ArF photoresist, and a preparation method and a photoetching method thereof.
Specifically, the invention provides a cubane-containing acrylate film-forming resin, wherein the cubane-containing acrylate film-forming resin is obtained by copolymerizing 20-60% of a unit monomer I and 40-80% of a unit monomer II, the unit monomer I has a structure shown in a formula (1), and the unit monomer II has a structure shown in a formula (2):
wherein R is1And R1Each independently being a hydrogen atom or a methyl group, R2Is an acid-labile group and has a structure selected from any one of the following structural formula series (3):
wherein, X is methyl or ethyl,
represents a bond to oxygen in the host structure.
Preferably, the unit monomer II is selected from at least one of the following substances: t-butanol (meth) acrylate, cyclopentanol (meth) acrylate, cyclohexanol (meth) acrylate, isoborneol (meth) acrylate, 2-methyl-2-adamantanol (meth) acrylate, 2-ethyl-2-adamantanol (meth) acrylate, t-butoxycarbonyl (meth) acrylate, tetrahydrofuran-2-hydroxy- (meth) acrylate, 2-carbonyl-tetrahydrofuran-3-hydroxy- (meth) acrylate, tetrahydropyran-2-hydroxy- (meth) acrylate, 2-carbonyl-tetrahydropyran-3-hydroxy- (meth) acrylate.
Preferably, the cubane-containing acrylate-based film-forming resin is a binary copolymer, a ternary copolymer or a quaternary copolymer.
Preferably, the cubane-containing acrylate-based film-forming resin has a weight average molecular weight of 15000 to 50000 and a molecular weight distribution of 1.5 to 3.0.
The invention also provides an ArF photoresist, which contains the acrylic ester film-forming resin containing cubane and a photoacid generator.
Preferably, the photoacid generator is an ionic photoacid generator which is an iodonium salt and/or a sulfonium salt and/or a nonionic photoacid generator selected from at least one of an organic halogen compound, diazosulfone, and an imidate.
Preferably, the ArF photoresist also contains additives and/or solvents.
Preferably, the content of the acrylate film-forming resin containing cubane is 10-35 wt%, the content of the photoacid generator is 0.5-5 wt%, and the total content of the additive and the solvent is 60-85 wt%, based on the total weight of the ArF photoresist.
Preferably, the additive is selected from at least one of a leveling agent, a plasticizer, a dissolution rate enhancer, and a photosensitizer, and the solvent is selected from at least one of cyclohexanone, diacetone alcohol, ethyl acetate, ethylene glycol monomethyl ether acetate, and dipropylene glycol monomethyl ether.
The preparation method of the ArF photoresist comprises the steps of uniformly mixing the acrylate film-forming resin containing the cubane, the photoacid generator and optional additives and solvents, and then sequentially filtering the mixture by using a first filter with the pore diameter of 20-50nm and a second filter with the pore diameter of 2-20nm, wherein the pore diameter of the first filter is larger than that of the second filter. The manner of the uniform mixing is not particularly limited in the present invention, and for example, the cubane-containing acrylate film-forming resin, the photoacid generator, and optional additives and solvents may be added to a clean plastic container, and then the plastic container is fixed on a mechanical oscillator and shaken at room temperature for 10 to 48 hours to fully dissolve the components.
As shown in fig. 1 b, the photolithography method provided by the present invention comprises:
coating an anti-reflection layer: coating an anti-reflective layer material on a wafer substrate (substrate) with a spin coater to form an anti-reflective layer (BARC);
glue homogenizing: coating the ArF photoresist on the surface of an anti-reflection layer to form a photoresist layer;
baking: baking the mixture in a hot plate cavity of the spin coater at 120-150 ℃ for 80-150 seconds;
and (3) cooling: cooling to room temperature in a cold plate cavity of the spin coater;
exposure: exposing by using a photoetching machine to copy the pattern on the mask plate onto the photoresist layer;
baking: baking the mixture in a hot plate cavity of the spin coater at 90-120 ℃ for 90-130 seconds;
and (3) developing: and completely developing and washing the exposed photoresist by using a developing machine.
Preferably, the photoresist is applied by spin coating.
Preferably, the photoresist layer has a thickness of 0.1 μm to 1.0 μm.
Preferably, the wavelength of the exposure is 193 nm.
The invention has the following beneficial effects: the ArF photoresist provided by the invention has better etching resistance, a hard mask layer (hard mask) is not needed in the photoetching process, and a new photoetching process is adopted to replace the hard mask process, so that the aim of saving the hard mask layer can be fulfilled, and the etching resistance equivalent to or even better than that of the original process can be achieved. In addition, the photoetching process provided by the invention only needs a rotary spin coater for subsequent photoetching, and does not need a CVD machine, thereby achieving the purposes of reducing material cost and production time.
Drawings
FIG. 1 is a diagram illustrating a conventional photolithography method and a photolithography method according to the present invention in comparison, wherein a is the conventional photolithography method and b is the photolithography method according to the present invention.
Detailed Description
The following detailed description of embodiments of the invention is intended to be illustrative of the invention and is not to be construed as limiting the invention. The examples do not specify particular techniques or conditions, and are performed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
In the following examples and comparative examples, specific synthetic methods of 4-hydroxymethyl-cubane-1-methoxymethacrylate are as follows, specifically: using cyclopentenone as raw material, substituting with NBS to produce 4-bromocyclopentyl-2-enone (a), and reacting with Br2Adding to generate 2,3, 4-tribromocyclopentanone (b), generating 2-bromocyclopentane-2, 4-dienone (c) through elimination reaction, then obtaining dimer (d) through intermolecular cycloaddition reaction, generating e through intramolecular cycloaddition reaction, generating f through Favorskii rearrangement reaction, generating cubane-1, 4-dimethanol (g) through reduction reaction, and finally generating target product 4-hydroxymethyl-cubane-1-methoxy methacrylate (h) through esterification reaction with methacrylic acid. Among them, the reactions (a) to (f) are conventional and reported in the prior patent literature.
Example 1
This example relates to the preparation of a cubane-containing acrylate-based film-forming resin (binary), the route being as follows:
51.0g of 4-hydroxymethyl-cubane-1-methoxy methacrylate, 35.0g of 2-methyl-2-adamantanol methacrylate, 2.0g of free radical polymerization initiator AIBN and 100g of solvent 1, 4-dioxane are sequentially added into a 500ml three-neck flask, nitrogen is introduced for 10 minutes under the stirring condition, and then the mixture is heated to 70 ℃ under the protection of nitrogen to react for 18 hours to obtain the film-forming resin. The film-forming resin had a weight average molecular weight of 42000 and a molecular weight distribution of 2.10.
The polymerization reaction formula is as follows:
example 2
This example relates to the preparation of a cubane-containing acrylate-based film-forming resin (ternary), the route being as follows:
30.6g of 4-hydroxymethyl-cubane-1-methoxy methacrylate, 39.9g of 2-carbonyl-tetrahydrofuran-3-hydroxy-methacrylate, 31.5g of 2-methyl-2-adamantanol methacrylate, 2.0g of free radical polymerization initiator AIBN and 180g of solvent 1, 4-dioxane are sequentially added into a 500ml three-neck flask, nitrogen is introduced for 10 minutes under the stirring condition, and then the mixture is heated to 80 ℃ under the protection of nitrogen to react for 16 hours, so that the film-forming resin is obtained. The weight average molecular weight of the film-forming resin was 32000, and the molecular weight distribution was 2.69.
The polymerization reaction formula is as follows:
example 3
This example relates to the preparation of a cubane-containing acrylate-based film-forming resin (quaternaries), the route is as follows:
20.2g of 4-hydroxymethyl-cubane-1-methoxy methacrylate, 40.5g of 2-carbonyl-tetrahydrofuran-3-hydroxy-methacrylate, 21.9g of 2-methyl-2-adamantanol methacrylate, 16.8g of 2-ethyl-2-adamantanol methacrylate, 2.0g of free radical polymerization initiator AIBN and 180g of solvent 1, 4-dioxane are sequentially added into a 500ml three-neck flask, nitrogen is introduced for 10 minutes under the stirring condition, and then the mixture is heated to 75 ℃ under the protection of nitrogen to react for 17 hours to obtain the film-forming resin. The film-forming resin had a weight average molecular weight of 37000 and a molecular weight distribution of 3.05.
The polymerization reaction formula is as follows:
example 4
This example is provided to illustrate an ArF photoresist and a method for preparing the same according to the present invention.
Raw materials: example 1 synthesized film-forming resin 28 wt%, photoacid generator (4, 4' -dimethyldiphenyliodonium hexafluorophosphate) 1.5 wt%, additive (polydimethylsiloxane) 2 wt%, and solvent (cyclohexanone) 68.5 wt%.
The above film-forming resin, photoacid generator, additive and solvent were added to a clean plastic container (250 ml polypropylene plastic bottle), and the plastic container was fixed on a mechanical oscillator, shaken at room temperature for 20 hours to sufficiently dissolve the components, and then filtered sequentially with a first filter having an aperture of 50nm and a second filter having an aperture of 10nm to obtain ArF photoresist J1.
Example 5
This example is provided to illustrate an ArF photoresist and a method for preparing the same according to the present invention.
Raw materials: example 2 synthesized film-forming resin 23 wt%, photoacid generator (4, 4' -dimethyldiphenyliodonium hexafluorophosphate) 2.5 wt%, additive (polydimethylsiloxane) 2 wt%, and solvent (diacetone alcohol) 72.5 wt%.
The above film-forming resin, photoacid generator, additive and solvent were added to a clean plastic container (250 ml polypropylene plastic bottle), and the plastic container was fixed on a mechanical oscillator, shaken at room temperature for 20 hours to sufficiently dissolve the components, and then filtered sequentially with a first filter having an aperture of 40nm and a second filter having an aperture of 5nm to obtain ArF photoresist J2.
Example 6
This example is provided to illustrate an ArF photoresist and a method for preparing the same according to the present invention.
Raw materials: example 3 synthesized film-forming resin 25 wt%, photoacid generator (4, 4' -dimethyldiphenyliodonium hexafluorophosphate) 3.0 wt%, additive (polydimethylsiloxane) 3 wt%, and solvent (ethyl acetate) 69 wt%.
The above film-forming resin, photoacid generator, additive and solvent were added to a clean plastic container (250 ml polypropylene plastic bottle), and the plastic container was fixed on a mechanical oscillator, shaken at room temperature for 20 hours to sufficiently dissolve the components, and then filtered sequentially with a first filter having an aperture of 30nm and a second filter having an aperture of 8nm to obtain ArF photoresist J3.
Comparative example 1
This comparative example serves to illustrate a reference ArF photoresist and a method of making the same.
An acrylate-based film-forming resin was prepared according to the method of example 1 and an ArF photoresist was prepared according to the method of example 4, except that the unit monomer i (4-hydroxymethyl-cubane-1-methoxymethacrylate) was replaced with the same weight part of 2-carbonyl-tetrahydrofuran-3-hydroxy-methacrylate during the preparation of the acrylate-based film-forming resin to obtain a reference ArF photoresist DJ 1.
Comparative example 2
This comparative example serves to illustrate a reference ArF photoresist and a method of making the same.
An acrylate-based film-forming resin was prepared according to the method of example 2 and an ArF photoresist was prepared according to the method of example 5, except that in the preparation of the acrylate-based film-forming resin, the unit monomer i (4-hydroxymethyl-cubane-1-methoxy methacrylate) was replaced with isoborneol methacrylate in the same weight part to obtain a reference ArF photoresist DJ 2.
Comparative example 3
This comparative example serves to illustrate a reference ArF photoresist and a method of making the same.
An acrylate-based film-forming resin was prepared according to the method of example 3 and an ArF photoresist was prepared according to the method of example 6, except that the unit monomer i (4-hydroxymethyl-cubane-1-methoxymethacrylate) was replaced with the same weight part of cyclohexanol methacrylate during the preparation of the acrylate-based film-forming resin to obtain a reference ArF photoresist DJ 3.
Test example 1
ArF photoresists J1-J3 from examples 4 to 6 and reference ArF photoresists DJ1-DJ3 from comparative examples 1 to 3 were spun onto different test wafers, which had been antireflective coated, using an ACT-8 spin coater at 1000 rpm. Thereafter, the test piece was baked at 120 ℃ for 150 seconds and cooled to room temperature. And measuring the thickness of the photoresist film layer.
Respectively placing more than one test piece into LAM EXELAN HPT etching machine under 60Mt/1000W/500W/45CF process conditions4/180Ar/100O2Etch for 20 seconds. And measuring the thickness of the residual photoresist film layer and calculating the etching rate of the film layer. Specific results are shown in table 1.
TABLE 1
As can be seen from the data in Table 1, the etch rates of ArF photoresists J1-J3 were all lower than the reference ArF photoresists DJ1-DJ3, indicating that the ArF photoresists comprising cubane-containing acrylate-based film-forming resins are more resistant to etching.
Test example 2
On a substrate test piece A which is provided with an anti-reflection layer, adopting ArF photoresist J1 obtained in the embodiment 4, and adopting the photoetching method described by the invention to expose and develop to prepare a patterned photoresist layer (the structure diagram is shown as b in figure 1), wherein the thickness of the photoresist layer is 370nm, the material of the substrate is silicon dioxide, and the thickness of the anti-reflection layer is 20 nm; and etching with the maskPreparing a lower film layer and a substrate to obtain a patterned substrate, measuring the line distance of the substrate pattern to be 86nm and the depth to be 124nm, wherein the etching is carried out by using a LAM EXELAN HPT etching machine under the process condition of 60Mt/1000W/500W/45CF4/180Ar/100O2Etch for 20 seconds.
On a substrate test piece B which is provided with a hard mask layer and an anti-reflection layer, a patterned photoresist layer (the structure diagram is shown as a in figure 1) is prepared by adopting a commercially available ArF photoresist through exposure and development, wherein the thickness of the photoresist is 150nm, the substrate material is silicon dioxide, the thickness of the anti-reflection layer is 20nm, and the hard mask layer is a composite layer of an amorphous carbon layer (the thickness is 200nm) and silicon oxynitride (the thickness is 300 nm); and etching the lower film layer by using the mask layer as a mask until a patterned hard mask layer is prepared, etching the substrate by using the hard mask layer as a mask to prepare the patterned substrate, and measuring the line distance of the substrate pattern to be 85nm and the depth to be 110nm, wherein the etching uses a LAM EXELAN HPT etching machine under the process condition of 60Mt/1000W/500W/45CF4/180Ar/100O2Etch for 20 seconds.
The above results show that the photoresist and the photolithography process thereof provided by the present invention can achieve the performance required by the hard mask process, so that the photoresist can be used to replace the hard mask layer by adjusting the thickness of the photoresist film layer.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (12)
1. The cubane-containing acrylate film-forming resin is characterized by being obtained by copolymerizing 20-60 mass percent of unit monomer I and 40-80 mass percent of unit monomer II, wherein the unit monomer I has a structure shown in a formula (1), and the unit monomer II has a structure shown in a formula (2):
wherein R is1And R1Each independently being a hydrogen atom or a methyl group, R2Is an acid-labile group and has a structure selected from any one of the following structural formula series (3):
wherein, X is methyl or ethyl,
represents a bond to oxygen in the host structure.
2. A cubane-containing acrylate film-forming resin according to claim 1, wherein the unit monomer ii is at least one selected from the group consisting of: t-butanol (meth) acrylate, cyclopentanol (meth) acrylate, cyclohexanol (meth) acrylate, isoborneol (meth) acrylate, 2-methyl-2-adamantanol (meth) acrylate, 2-ethyl-2-adamantanol (meth) acrylate, t-butoxycarbonyl (meth) acrylate, tetrahydrofuran-2-hydroxy- (meth) acrylate, 2-carbonyl-tetrahydrofuran-3-hydroxy- (meth) acrylate, tetrahydropyran-2-hydroxy- (meth) acrylate, 2-carbonyl-tetrahydropyran-3-hydroxy- (meth) acrylate.
3. The cubane-containing acrylate-based film-forming resin according to claim 1 or 2, wherein the cubane-containing acrylate-based film-forming resin is a binary copolymer, a terpolymer or a tetrapolymer; the weight average molecular weight of the acrylic ester film-forming resin containing the cubane is 15000-50000, and the molecular weight distribution is 1.5-3.0.
4. An ArF photoresist comprising the cubane-containing acrylate film-forming resin according to any one of claims 1 to 3 and a photoacid generator.
5. The ArF photoresist of claim 4, wherein the photoacid generator is an ionic photoacid generator and/or a non-ionic photoacid generator, the ionic photoacid generator is an iodonium salt and/or a sulfonium salt, and the non-ionic photoacid generator is at least one selected from an organic halogen compound, a diazosulfone, and an imidosulfonate.
6. The ArF photoresist according to claim 4, further comprising an additive and/or a solvent.
7. The ArF photoresist of claim 6, wherein the content of the cubane-containing acrylate film-forming resin is 10-35 wt%, the content of the photoacid generator is 0.5-5 wt%, and the total content of the additive and the solvent is 60-85 wt%, based on the total weight of the ArF photoresist.
8. The ArF photoresist according to claim 6, wherein the additive is at least one selected from a leveling agent, a plasticizer, a dissolution rate enhancer, and a photosensitizer, and the solvent is at least one selected from cyclohexanone, diacetone alcohol, ethyl acetate, ethylene glycol monomethyl ether acetate, and dipropylene glycol monomethyl ether.
9. The method of preparing ArF photoresist according to any one of claims 4 to 8, comprising uniformly mixing the cubane-containing acrylate-based film-forming resin, the photoacid generator, and optionally additives and solvents, followed by sequentially filtering with a first filter having a pore size of 20 to 50nm and a second filter having a pore size of 2 to 20nm, the pore size of the first filter being larger than that of the second filter.
10. A lithographic method, comprising:
coating an anti-reflection layer: coating an anti-reflection layer material on a wafer substrate by using a spin coater to form an anti-reflection layer;
glue homogenizing: coating ArF photoresist of any one of claims 4 to 8 on the surface of the anti-reflection layer to form a photoresist layer;
baking: baking the mixture in a hot plate cavity of the spin coater at 120-150 ℃ for 80-150 seconds;
and (3) cooling: cooling to room temperature in a cold plate cavity of the spin coater;
exposure: exposing by using a photoetching machine to copy the pattern on the mask plate onto the photoresist layer;
baking: baking the mixture in a hot plate cavity of the spin coater at 90-120 ℃ for 90-130 seconds;
and (3) developing: and completely developing and washing the exposed photoresist by using a developing machine.
11. The lithographic method of claim 10, wherein the photoresist is applied by spin coating.
12. The lithographic method of claim 10, wherein the photoresist layer has a thickness of 0.1 μ ι η to 1.0 μ ι η; the wavelength of the exposure is 193 nm.
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| CN117631438B (en) * | 2023-11-28 | 2024-11-22 | 福建泓光半导体材料有限公司 | Hard mask composition and method for forming pattern |
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