CN117304394B - Polymer for photoresist top layer coating, preparation method and application - Google Patents
Polymer for photoresist top layer coating, preparation method and application Download PDFInfo
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- CN117304394B CN117304394B CN202311609279.9A CN202311609279A CN117304394B CN 117304394 B CN117304394 B CN 117304394B CN 202311609279 A CN202311609279 A CN 202311609279A CN 117304394 B CN117304394 B CN 117304394B
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- 229920000642 polymer Polymers 0.000 title claims abstract description 100
- 229920002120 photoresistant polymer Polymers 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 238000000576 coating method Methods 0.000 title claims abstract description 18
- 239000011248 coating agent Substances 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000007654 immersion Methods 0.000 claims abstract description 15
- 239000000178 monomer Substances 0.000 claims description 116
- 238000006243 chemical reaction Methods 0.000 claims description 45
- 239000011259 mixed solution Substances 0.000 claims description 35
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 30
- WVYWICLMDOOCFB-UHFFFAOYSA-N 4-methyl-2-pentanol Chemical compound CC(C)CC(C)O WVYWICLMDOOCFB-UHFFFAOYSA-N 0.000 claims description 23
- 239000003999 initiator Substances 0.000 claims description 22
- 150000003254 radicals Chemical class 0.000 claims description 22
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 15
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 15
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 15
- QTKPMCIBUROOGY-UHFFFAOYSA-N 2,2,2-trifluoroethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)F QTKPMCIBUROOGY-UHFFFAOYSA-N 0.000 claims description 14
- MTLWTRLYHAQCAM-UHFFFAOYSA-N 2-[(1-cyano-2-methylpropyl)diazenyl]-3-methylbutanenitrile Chemical compound CC(C)C(C#N)N=NC(C#N)C(C)C MTLWTRLYHAQCAM-UHFFFAOYSA-N 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 9
- 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 claims description 8
- 230000008569 process Effects 0.000 claims description 6
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 5
- XYVQFUJDGOBPQI-UHFFFAOYSA-N Methyl-2-hydoxyisobutyric acid Chemical compound COC(=O)C(C)(C)O XYVQFUJDGOBPQI-UHFFFAOYSA-N 0.000 claims description 5
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 5
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 claims description 4
- CUDYYMUUJHLCGZ-UHFFFAOYSA-N 2-(2-methoxypropoxy)propan-1-ol Chemical compound COC(C)COC(C)CO CUDYYMUUJHLCGZ-UHFFFAOYSA-N 0.000 claims description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 125000005395 methacrylic acid group Chemical group 0.000 claims description 3
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 claims 1
- 238000002386 leaching Methods 0.000 abstract description 9
- 230000003287 optical effect Effects 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- 239000000203 mixture Substances 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 238000001816 cooling Methods 0.000 description 13
- 239000007787 solid Substances 0.000 description 13
- 238000001035 drying Methods 0.000 description 12
- 238000001914 filtration Methods 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 230000001376 precipitating effect Effects 0.000 description 12
- 238000005086 pumping Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 230000003068 static effect Effects 0.000 description 5
- 239000008199 coating composition Substances 0.000 description 4
- 230000005855 radiation Effects 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- GXZZZWUTJCPYHC-UHFFFAOYSA-M (4-tert-butylphenyl)-diphenylsulfanium;1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F.C1=CC(C(C)(C)C)=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 GXZZZWUTJCPYHC-UHFFFAOYSA-M 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000001459 lithography Methods 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 235000012431 wafers Nutrition 0.000 description 2
- FQDXJYBXPOMIBX-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoro-2-methylpropan-2-ol Chemical group FC(F)(F)C(O)(C)C(F)(F)F FQDXJYBXPOMIBX-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000000589 high-performance liquid chromatography-mass spectrometry Methods 0.000 description 1
- 238000000671 immersion lithography Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- SXKLNBJCHYEPDL-UHFFFAOYSA-N n,n-difluorosulfamoyl fluoride Chemical group FN(F)S(F)(=O)=O SXKLNBJCHYEPDL-UHFFFAOYSA-N 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000003362 replicative effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 238000002834 transmittance 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
- C08F220/22—Esters containing halogen
- C08F220/24—Esters containing halogen containing perhaloalkyl radicals
-
- 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
- C08F220/38—Esters containing sulfur
- C08F220/387—Esters containing sulfur and containing nitrogen and oxygen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
- C09D133/16—Homopolymers or copolymers of esters containing halogen atoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to the technical field of photoresist, in particular to a polymer for a photoresist top layer coating, a preparation method and application thereof, wherein the photoresist is 193nm immersion photoresist, and the polymer has the following structure:the method comprises the steps of carrying out a first treatment on the surface of the x, y, z, w are the mass fractions of the repeating units in the polymer, x is selected from 30-80%, y is selected from 10-50%, z is selected from 1-20%, w is selected from 1-20%, the molecular weight of the polymer is selected from 2000-50000Da, and PDI is selected from 1.0-4.0. The polymer is applied to 193nm immersion photoresist top coat. The polymer can effectively reduce the pollution degree of the photoacid generator to an optical lens during immersion exposure, can increase the contact angle of a photoresist top layer coating, and has little leaching amount of the photoacid generator.
Description
Technical Field
The invention relates to a polymer for a photoresist top layer coating, a preparation method and application thereof, and belongs to the technical field of photoresists.
Background
Photoresist is a photosensitive film that can be used to replicate a pattern on a mask onto a substrate, the photoresist coating formed on the substrate being fully exposed to active radiation through a mask, the mask being selective for the transmission of the active radiation, portions of the mask being impermeable to the active radiation. The photo-induced chemical conversion of the photoresist coating exposed to the activating radiation occurs, thereby replicating the image from the mask onto the substrate. The exposed photoresist coating is baked and contacted with a developer solution to complete development, thereby obtaining a relief image that allows selective processing of the substrate.
Photolithography is an important process for fabricating large scale integrated circuits, which has undergone the development of techniques from G-line (436 nm), I-line (365 nm), krF (248 nm), arF (193 nm), EUV (13.5 nm), and so on. Among them, arF lithography machines use excimer lasers as light sources, and their lithography technology is becoming mature and applied extremely widely.
ArF immersion lithography uses water to expose the photoresist, however, when the photoresist is contacted with water, a small amount of photoacid generator component will leach into the water, so that the optical lens is contaminated and the effective refractive index and transmittance properties of the immersion fluid will change, and to prevent or mitigate this, a topcoat composition is used over the photoresist as a barrier to the immersion fluid and photoresist layer. However, as the refractive index, thickness, interaction with the underlying photoresist, and immersion time of the top layer coating change, the lithographic process window, critical dimensions, and topography also change.
To obtain a top coat composition with good properties, a top coat polymer with a high receding angle should be designed upon immersion exposure. Therefore, research and development of a photoresist with a high back-off angle has great significance for the development of photoresist technology.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a polymer for a photoresist top layer coating, a preparation method and application thereof, wherein the top layer coating composition prepared from the polymer has higher receding angle and has extremely low leaching amount of a photoacid generator.
The technical scheme for solving the technical problems is as follows: a polymer for a photoresist topcoat, the photoresist being a 193nm immersion photoresist, the polymer having the structure of formula I:
a formula I;
x, y, z, w are the mass fractions of the repeating units in the polymer, x is selected from 30-80%, y is selected from 10-50%, z is selected from 1-20%, w is selected from 1-20%, the molecular weight of the polymer is selected from 2000-50000Da, and PDI is selected from 1.0-4.0.
Further, x is selected from 45-55%, y is selected from 15-25%, z is selected from 5-15%, and w is selected from 5-15%.
Further, the molecular weight of the polymer is selected from 8000-25000Da and PDI is selected from 1.5-2.5.
The invention also discloses a preparation method of the polymer for the photoresist top layer coating, which comprises the following steps: dissolving a monomer and a free radical initiator in an electronic grade solvent to obtain a mixed solution, dripping the mixed solution into the electronic grade solvent under the atmosphere of inert gas to form a reaction system, controlling the reaction temperature and the reaction time, and obtaining a polymer solution after the reaction is finished;
the monomer comprises a monomer A, a monomer B, a monomer C and a monomer D; the monomer A is 4, 4-trifluoro-3-hydroxy-1- (2-methylpropyl) -3- (trifluoromethyl) butyl-2-methyl-2-acrylic acid, and the monomer B is 2- [ [ (trifluoromethyl) sulfonyl ] amino ] ethyl-2-methyl-2-acrylic acid; the monomer C is methacrylic acid-1, 2-tetramethyl propyl ester; the monomer D is trifluoroethyl methacrylate.
Further, the free radical initiator is any one of benzoyl peroxide, azodiisobutyronitrile, benzoyl peroxide tert-butyl ester, dimethyl azodiisobutyrate, azodiisovaleronitrile and azodiisoheptanenitrile.
Preferably, the free radical initiator is azobisisovaleronitrile.
Further, the electronic grade solvent is any one of methyl 2-hydroxyisobutyrate, propylene glycol methyl ether, methyl isobutyl carbinol, propylene glycol monomethyl ether acetate and dipropylene glycol methyl ether.
Preferably, the electronic grade solvent is methyl isobutyl carbinol.
Further, the free radical initiator is used in an amount of 1 to 10% of the total mass of the monomers; the mass concentration of the monomer and the free radical initiator in the mixed solution is 40-80%, and the mass concentration of the monomer and the free radical initiator in the reaction system is 15-55%.
Preferably, the free radical initiator is used in an amount of 2 to 6% of the total mass of the monomers; the mass concentration of the monomer and the free radical initiator in the mixed solution is 55-65%, and the mass concentration of the monomer and the free radical initiator in the reaction system is 25-45%.
Further, the reaction temperature is 55-130 ℃ and the reaction time is 1-12 hours.
Preferably, the reaction temperature is 70-100 ℃ and the reaction time is 4-8 hours.
The invention also discloses application of the polymer for the photoresist top layer coating, and the polymer is applied to 193nm immersion photoresist top layer coating.
The beneficial effects of the invention are as follows:
1) The polymer consists of four units, the transparency at 193nm is very high, and the trifluoro sulfonamide group contained enables the polymer to have better alkali solubility, so that the dissolution rate of the polymer in a developer is greatly enhanced, a higher dynamic contact angle can be maintained, and the leaching amount of the photoacid generator is very small;
2) The polymer structure contains hexafluorotertiary butanol groups, so that the contact angle between the polymer structure and water can be increased;
3) The polymer structure contains acid-unstable groups, which is helpful for improving the solubility of the developer in the exposed area and improving the dynamic contact angle;
4) The preparation method of the polymer is simple and convenient.
Drawings
FIG. 1 is a schematic diagram of H of Polymer D in the examples 1 -NMR spectrum.
Detailed Description
The following describes the present invention in detail. The present invention may be embodied in many other forms than described herein and similarly modified by those skilled in the art without departing from the spirit of the invention, so that the invention is not limited to the specific embodiments disclosed.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
A polymer for a photoresist topcoat, the photoresist being a 193nm immersion photoresist, the polymer having the structure of formula I:
a formula I;
x, y, z, w are the mass fractions of the repeating units in the polymer, x is selected from 30-80%, y is selected from 10-50%, z is selected from 1-20%, w is selected from 1-20%, the molecular weight of the polymer is selected from 2000-50000Da, and PDI is selected from 1.0-4.0.
More specifically, x is selected from 45-55%, y is selected from 15-25%, z is selected from 5-15%, and w is selected from 5-15%.
More particularly, the molecular weight of the polymer is selected from 8000-25000Da and the PDI is selected from 1.5-2.5.
A method for preparing a polymer for a photoresist top layer coating, the method comprising: dissolving a monomer and a free radical initiator in an electronic grade solvent to obtain a mixed solution, dripping the mixed solution into the electronic grade solvent under the atmosphere of inert gas to form a reaction system, controlling the reaction temperature and the reaction time, and obtaining a polymer solution after the reaction is finished;
the monomer comprises a monomer A, a monomer B, a monomer C and a monomer D; the monomer A is 4, 4-trifluoro-3-hydroxy-1- (2-methylpropyl) -3- (trifluoromethyl) butyl-2-methyl-2-acrylic acid, and the monomer B is 2- [ [ (trifluoromethyl) sulfonyl ] amino ] ethyl-2-methyl-2-acrylic acid; the monomer C is methacrylic acid-1, 2-tetramethyl propyl ester; the monomer D is trifluoroethyl methacrylate.
Specifically, the free radical initiator is any one of benzoyl peroxide, azodiisobutyronitrile, benzoyl peroxide tert-butyl ester, dimethyl azodiisobutyrate, azodiisovaleronitrile and azodiisoheptanenitrile.
Specifically, the electronic grade solvent is any one of methyl 2-hydroxyisobutyrate, propylene glycol methyl ether, methyl isobutyl methanol, propylene glycol monomethyl ether acetate and dipropylene glycol methyl ether.
Specifically, the dosage of the free radical initiator is 1-10% of the total mass of the monomers; the mass concentration of the monomer and the free radical initiator in the mixed solution is 40-80%, and the mass concentration of the monomer and the free radical initiator in the reaction system is 15-55%.
Specifically, in the monomers, the mass fraction of the monomer A is selected from 30-80%, preferably 45-55%; the mass fraction of the monomers B is selected from 10 to 50%, preferably 15 to 25%; the mass fraction of monomer C is selected from 1-20%, preferably 5-15%; the mass fraction of monomer D is selected from 1 to 20%, preferably 5 to 15%.
Preferably, the free radical initiator is used in an amount of 2 to 6% of the total mass of the monomers; the mass concentration of the monomer and the free radical initiator in the mixed solution is 55-65%, and the mass concentration of the monomer and the free radical initiator in the reaction system is 25-45%.
Specifically, the reaction temperature is 55-130 ℃, and the reaction time is 1-12 hours.
Preferably, the reaction temperature is 70-100 ℃ and the reaction time is 4-8 hours.
Use of a polymer for a photoresist topcoat, the polymer being used in 193nm immersion photoresist topcoat.
The monomers used in the polymer structures according to the examples of the present invention are shown in Table 1 below:
TABLE 1 monomer names and Structure
Polymer preparation examples:
example 1
Preparation of a polymer for photoresist topcoat (preparation of polymer a):
70.0g of electronic grade methyl isobutyl carbinol was charged into a 500mL reactor and was maintained under nitrogen for 30min.
A mixed solution was prepared by dissolving 54.0g of monomer A (4, 4-trifluoro-3-hydroxy-1- (2-methylpropyl) -3- (trifluoromethyl) butyl-2-methyl-2-acrylic acid), 18.0g of monomer B (2- [ [ (trifluoromethyl) sulfonyl ] amino ] ethyl-2-methyl-2-acrylic acid), 4.0g of monomer C (1, 2-tetramethyl-propyl methacrylate), 4.0g of monomer D (trifluoroethyl methacrylate), and 2.5g of azobisisovaleronitrile in 50.0g of electronic grade methyl isobutyl methanol.
And (3) pumping the mixed solution into the 500mL reactor by using a metering pump, controlling the reaction temperature to be 80-85 ℃, preserving the heat for 5 hours, cooling the system to room temperature after the reaction is completed, slowly dripping the system into 1000.0g of water, precipitating white solid, filtering and drying to obtain 52.0g of polymer A, wherein the yield is 65.0%, mw=19472Da, and PDI=1.88.
Example 2
Preparation of a polymer for photoresist topcoat (preparation of Polymer B):
98.6g of electronic grade methyl isobutyl carbinol was charged into a 500mL reactor and allowed to stand under nitrogen for 30min.
A mixed solution was prepared by dissolving 50.0g of monomer A (4, 4-trifluoro-3-hydroxy-1- (2-methylpropyl) -3- (trifluoromethyl) butyl-2-methyl-2-acrylic acid), 14.0g of monomer B (2- [ [ (trifluoromethyl) sulfonyl ] amino ] ethyl-2-methyl-2-acrylic acid), 8.0g of monomer C (1, 2-tetramethyl-propyl methacrylate), 8.0g of monomer D (trifluoroethyl methacrylate), and 2.5g of azobisisovaleronitrile in 50.0g of electronic grade methyl isobutyl methanol.
And (3) pumping the mixed solution into the 500mL reactor by using a metering pump, controlling the reaction temperature to be 80-85 ℃, preserving the heat for 5 hours, cooling the system to room temperature after the reaction, slowly dripping the system into 1143.0g of water, precipitating white solid, filtering and drying to obtain 51.3.0g of polymer B with the yield of 64.1%, mw=16423 Da and PDI=1.86.
Example 3
Preparation of a polymer for photoresist topcoat (preparation of Polymer C):
136.7g of electronic grade methyl isobutyl carbinol was charged into a 500mL reactor and was maintained under nitrogen for 30min.
A mixed solution was prepared by dissolving 44.0g of monomer A (4, 4-trifluoro-3-hydroxy-1- (2-methylpropyl) -3- (trifluoromethyl) butyl-2-methyl-2-acrylic acid), 16.0g of monomer B (2- [ [ (trifluoromethyl) sulfonyl ] amino ] ethyl-2-methyl-2-acrylic acid), 10.0g of monomer C (1, 2-tetramethyl-propyl methacrylate), 10.0g of monomer D (trifluoroethyl methacrylate), and 2.5g of azobisisovaleronitrile in 50.0g of electronic grade methyl isobutyl methanol.
And (3) pumping the mixed solution into the 500mL reactor by using a metering pump, controlling the reaction temperature to be 80-85 ℃, preserving the heat for 5 hours, cooling the system to room temperature after the reaction, slowly dripping the system into 1333.0g of water, precipitating white solid, filtering and drying to obtain 46.6g of polymer C, wherein the yield is 58.3%, the Mw=15784 Da, and the PDI=1.83.
Example 4
Preparation of a polymer for photoresist topcoat (preparation of Polymer D):
136.7g of electronic grade methyl isobutyl carbinol was charged into a 500mL reactor and was maintained under nitrogen for 30min.
A mixed solution was prepared by dissolving 40.0g of monomer A (4, 4-trifluoro-3-hydroxy-1- (2-methylpropyl) -3- (trifluoromethyl) butyl-2-methyl-2-acrylic acid), 16.0g of monomer B (2- [ [ (trifluoromethyl) sulfonyl ] amino ] ethyl-2-methyl-2-acrylic acid), 12.0g of monomer C (1, 2-tetramethyl-propyl methacrylate), 12.0g of monomer D (trifluoroethyl methacrylate), and 3.0g of azobisisovaleronitrile in 50.0g of electronic grade methyl isobutyl methanol.
And (3) pumping the mixed solution into the 500mL reactor by using a metering pump, controlling the reaction temperature to be 80-85 ℃, preserving the heat for 5 hours, cooling the system to room temperature after the reaction, slowly dripping the system into 1333.0g of water, precipitating white solid, filtering and drying to obtain 46.4g of polymer D, wherein the yield is 58.0%, mw=12726Da and PDI=1.81. H of Polymer D 1 The NMR spectrum is shown in FIG. 1.
Example 5
Preparation of a polymer for photoresist topcoat (preparation of Polymer E):
120.0g of electronic grade methyl 2-hydroxyisobutyrate was charged into a 500mL reactor and maintained under nitrogen for 30min.
A mixed solution was prepared by dissolving 24.0g of monomer A (4, 4-trifluoro-3-hydroxy-1- (2-methylpropyl) -3- (trifluoromethyl) butyl-2-methyl-2-acrylic acid), 40.0g of monomer B (2- [ [ (trifluoromethyl) sulfonyl ] amino ] ethyl-2-methyl-2-acrylic acid), 0.8g of monomer C (1, 2-tetramethyl-propyl methacrylate), 15.2g of monomer D (trifluoroethyl methacrylate), and 0.8g of azobisisobutyronitrile in 120.0g of electronic grade 2-hydroxyisobutyric acid methyl ester.
And (3) pumping the mixed solution into the 500mL reactor by using a metering pump, controlling the reaction temperature to be 65-70 ℃, preserving the heat for 12 hours, cooling the system to room temperature after the reaction, slowly dripping the system into 1333.0g of water, precipitating white solid, filtering and drying to obtain 44.8g of polymer E, the yield is 56.0%, the Mw=37627 Da, and the PDI=1.90.
Example 6
Preparation of a polymer for photoresist topcoat (preparation of Polymer F):
76.6g of electronic grade propylene glycol methyl ether was charged into a 500mL reactor and maintained under nitrogen for 30min.
A mixed solution was prepared by dissolving 64.0g of monomer A (4, 4-trifluoro-3-hydroxy-1- (2-methylpropyl) -3- (trifluoromethyl) butyl-2-methyl-2-acrylic acid), 8.0g of monomer B (2- [ [ (trifluoromethyl) sulfonyl ] amino ] ethyl-2-methyl-2-acrylic acid), 7.2g of monomer C (1, 2-tetramethyl-propyl methacrylate), 0.8g of monomer D (trifluoroethyl methacrylate) and 4.0g of azobisisobutyronitrile in 21.2g of electronic grade propylene glycol methyl ether.
And (3) pumping the mixed solution into the 500mL reactor by using a metering pump, controlling the reaction temperature to be 90-95 ℃, preserving the heat for 4 hours, cooling the system to room temperature after the reaction, slowly dripping the system into 888.9g of water, precipitating a white solid, filtering and drying to obtain 52.6g of polymer F, wherein the yield is 65.8%, the Mw=12224Da, and the PDI=1.80.
Example 7
Preparation of a polymer for photoresist topcoat (preparation of Polymer G):
333.3g of electronic grade propylene glycol monomethyl ether acetate were charged to the reactor and kept under nitrogen for 30min.
A mixed solution was prepared by dissolving 36.0g of monomer A (4, 4-trifluoro-3-hydroxy-1- (2-methylpropyl) -3- (trifluoromethyl) butyl-2-methyl-2-acrylic acid), 12.0g of monomer B (2- [ [ (trifluoromethyl) sulfonyl ] amino ] ethyl-2-methyl-2-acrylic acid), 16.0g of monomer C (1, 2-tetramethyl-propyl methacrylate), 16.0g of monomer D (trifluoroethyl methacrylate), and 0.8g of dimethyl azodiisobutyrate in 66.7g of electronic grade propylene glycol monomethyl ether acetate.
And (3) pumping the mixed solution into the reactor by using a metering pump, controlling the reaction temperature to be 120-125 ℃, preserving the heat for 1 hour, cooling the system to room temperature after the reaction, slowly dripping the system into 2000.0G of water, precipitating white solid, filtering and drying to obtain 41.7G of polymer G with the yield of 52.1%, mw=13814Da and PDI=1.83.
Example 8
Preparation of a polymer for photoresist topcoat (preparation of Polymer H):
16.0g of electronic grade methyl isobutyl carbinol was charged into the reactor and was maintained under nitrogen for 30min.
A mixed solution was prepared by dissolving 44.0g of monomer A (4, 4-trifluoro-3-hydroxy-1- (2-methylpropyl) -3- (trifluoromethyl) butyl-2-methyl-2-acrylic acid), 20.0g of monomer B (2- [ [ (trifluoromethyl) sulfonyl ] amino ] ethyl-2-methyl-2-acrylic acid), 4.0g of monomer C (1, 2-tetramethyl-propyl methacrylate), 12.0g of monomer D (trifluoroethyl methacrylate), and 8.0g of azobisisovaleronitrile in 49.5g of electronic grade methyl isobutyl methanol.
And (3) pumping the mixed solution into the reactor by using a metering pump, controlling the reaction temperature to be 60-70 ℃, preserving the heat for 8 hours, cooling the system to room temperature after the reaction is finished, slowly dripping the system into 727.3g of water, precipitating white solid, filtering and drying to obtain 52.3g of polymer H with the yield of 65.4%, mw=14530 Da and PDI=1.84.
Comparative example 1
Polymer A1 was prepared by the same method as in example 1, except that the amount of monomer B used was outside the range defined in the present invention (the proportion of monomer B in the present comparative example was 55% by mass based on the total mass of the monomers), and the specific procedure was as follows:
preparation of polymer for photoresist topcoat (preparation of polymer A1):
70.0g of electronic grade methyl isobutyl carbinol was charged into a 500mL reactor and was maintained under nitrogen for 30min.
A mixed solution was prepared by dissolving 28.0g of monomer A (4, 4-trifluoro-3-hydroxy-1- (2-methylpropyl) -3- (trifluoromethyl) butyl-2-methyl-2-acrylic acid), 44.0g of monomer B (2- [ [ (trifluoromethyl) sulfonyl ] amino ] ethyl-2-methyl-2-acrylic acid), 4.0g of monomer C (1, 2-tetramethyl-propyl methacrylate), 4.0g of monomer D (trifluoroethyl methacrylate), and 2.5g of azobisisovaleronitrile in 50.0g of electronic grade methyl isobutyl methanol.
And (3) pumping the mixed solution into the 500mL reactor by using a metering pump, controlling the reaction temperature to be 80-85 ℃, preserving the heat for 5 hours, cooling the system to room temperature after the reaction is completed, slowly dripping the system into 1000.0g of water, precipitating white solid, filtering and drying to obtain 50.8g of polymer A, wherein the yield is 63.5%, the Mw=17724Da, and the PDI=1.86.
Comparative example 2
Polymer A2 was prepared in the same manner as in example 1, except that the amount of monomer B used was less than in the present invention
The specific procedure is as follows (the proportion of monomer B to the total mass of monomers in this comparative example is 8.75%).
Preparation of polymer for photoresist topcoat (preparation of polymer A2):
70.0g of electronic grade methyl isobutyl carbinol was charged into a 500mL reactor and was maintained under nitrogen for 30min.
A mixed solution was prepared by dissolving 64.0g of monomer A (4, 4-trifluoro-3-hydroxy-1- (2-methylpropyl) -3- (trifluoromethyl) butyl-2-methyl-2-acrylic acid), 7.0g of monomer B (2- [ [ (trifluoromethyl) sulfonyl ] amino ] ethyl-2-methyl-2-acrylic acid), 5.0g of monomer C (1, 2-tetramethyl-propyl methacrylate), 4.0g of monomer D (trifluoroethyl methacrylate), and 2.5g of azobisisovaleronitrile in 50.0g of electronic grade methyl isobutyl methanol.
And (3) pumping the mixed solution into the 500mL reactor by using a metering pump, controlling the reaction temperature to be 80-85 ℃, preserving the heat for 5 hours, cooling the system to room temperature after the reaction, slowly dripping the system into 1000.0g of water, precipitating white solid, filtering and drying to obtain 48.9g of polymer A, wherein the yield is 61.1%, mw=21659 Da, and PDI=1.96.
Comparative example 3
Polymer A3 was prepared by the same procedure as in example 1, except that monomer D was not added,the specific process is as follows:
preparation of polymer for photoresist topcoat (preparation of polymer A3):
70.0g of electronic grade methyl isobutyl carbinol was charged into a 500mL reactor and was maintained under nitrogen for 30min.
A mixed solution was prepared by dissolving 54.0g of monomer A (4, 4-trifluoro-3-hydroxy-1- (2-methylpropyl) -3- (trifluoromethyl) butyl-2-methyl-2-acrylic acid), 18.0g of monomer B (2- [ [ (trifluoromethyl) sulfonyl ] amino ] ethyl-2-methyl-2-acrylic acid), 8.0g of monomer C (1, 2-tetramethylpropyl methacrylate), and 2.5g of azobisisovaleronitrile in 50.0g of electronic grade methyl isobutyl methanol.
And (3) pumping the mixed solution into the 500mL reactor by using a metering pump, controlling the reaction temperature to be 80-85 ℃, preserving the heat for 5 hours, cooling the system to room temperature after the reaction, slowly dripping the system into 1000.0g of water, precipitating white solid, filtering and drying to obtain 53.6g of polymer A, wherein the yield is 67.0%, mw=19858 Da, and PDI=1.86.
Comparative example 4
Polymer A4 was prepared by the same procedure as in example 1, except that monomer D was used in an amount greater than in the present invention The amount defined (22% of monomer D in the present comparative example based on the total mass of the monomers),concrete embodimentsThe process is as follows:
preparation of polymer for photoresist topcoat (preparation of polymer A4):
70.0g of electronic grade methyl isobutyl carbinol was charged into a 500mL reactor and was maintained under nitrogen for 30min.
A mixed solution was prepared by dissolving 40.4g of monomer A (4, 4-trifluoro-3-hydroxy-1- (2-methylpropyl) -3- (trifluoromethyl) butyl-2-methyl-2-acrylic acid), 18.0g of monomer B (2- [ [ (trifluoromethyl) sulfonyl ] amino ] ethyl-2-methyl-2-acrylic acid), 4.0g of monomer C (1, 2-tetramethyl-propyl methacrylate), 17.6g of monomer D (trifluoroethyl methacrylate), and 2.5g of azobisisovaleronitrile in 50.0g of electronic grade methyl isobutyl methanol.
And (3) pumping the mixed solution into the 500mL reactor by using a metering pump, controlling the reaction temperature to be 80-85 ℃, preserving the heat for 5 hours, cooling the system to room temperature after the reaction, slowly dripping the system into 1000.0g of water, precipitating white solid, filtering and drying to obtain 4.3 g of polymer A, wherein the yield is 64.1%, mw=15867Da, and PDI=1.82.
The top coat composition is formulated: solutions of the polymers prepared in the above examples and comparative examples were formulated with photoacid generators (diphenyl 4-t-butylphenyl sulfonium nonafluorobutane sulfonate, CAS: 258872-05-8), electronic grade solvent methyl isobutyl carbinol to 193nm immersion photoresist topcoat compositions of varying solids content, the topcoat composition formulations being shown in Table 2.
Table 2 top coat composition formulation
Top coat composition performance test:
the top coating compositions in Table 2 were spin coated on silicon wafers (6 inches) at rotational speeds of 0rpm/10s, 200rpm/2s, 0rpm/2s, 1500rpm/30s, respectively, and the silicon wafers coated with the top coating compositions were placed on a hot plate at a temperature of 90℃for 1 minute, baked, and then immediately placed on a cold plate for cooling. The n-value (refractive index), k-value (absorbance coefficient), static contact angle, dynamic contact angle and leaching of photoacid generator in water were tested. The test instrument is as follows:
n value, k value: ellipsometer (brand/model: woollam/RC 2)
Static contact angle, dynamic contact angle: contact angle measuring instrument (brand/model: german Kelu upper/DSA 25S)
Leaching the photoacid generator in water: HPLC-MS (brand/model: agilent 1260/6420)
The specific test results are shown in Table 3.
TABLE 3 results of Top coating composition Performance test
As can be seen from the data in Table 3, compositions 1-16 employing the polymers of the present invention are all transparent at 193nm, i.e., k values of 0, have relatively large contact angles with water, and have very low photoacid generator leaching values. It is noted that the static contact angle and the (advancing) dynamic contact angle of the composition 7, the composition 8, the composition 11 and the composition 12 with water are all larger than 90 degrees, and the leaching value of the photoacid generator is also smaller than 1ppb, so that the pollution degree of the photoacid generator to a lens during 193nm immersion photoresist exposure can be greatly reduced, and the shape and the critical dimension of a pattern can be greatly improved.
As can be seen from the comparison of the data of compositions 1-2 with the data of comparative compositions 1-4, if the amount of monomer B is increased or decreased, the static contact angle, (advancing) dynamic contact angle and photoacid generator leaching value of the final composition are affected, and therefore, the polymer obtained by compounding the appropriate amount of monomer B with the other monomers defined in the invention is more beneficial for application in top-layer coatings. As can be seen from the comparison of the data of compositions 1-2 and comparative compositions 5-8, if the polymer does not contain monomer D or the amount of monomer D is inappropriate, the static contact angle, (advancing) dynamic contact angle and photoacid generator leaching value of the final composition are affected, and therefore, the polymer obtained by compounding the appropriate amount of monomer D with the other monomers defined in the invention is more beneficial for application in top-layer coatings.
The technical features of the above-described embodiments may be arbitrarily combined, and in order to simplify the description, all possible combinations of the technical features in the above-described embodiments are not exhaustive, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the invention as defined in the appended claims.
Claims (10)
1. A polymer for a photoresist topcoat, wherein the photoresist is a 193nm immersion photoresist, and wherein the polymer has the structure of formula I:
a formula I;
x, y, z, w are the mass fractions of the repeating units in the polymer, x is selected from 30-80%, y is selected from 10-50%, z is selected from 1-20%, w is selected from 1-20%, the molecular weight of the polymer is selected from 2000-50000Da, and PDI is selected from 1.0-4.0.
2. A polymer for a photoresist topcoat layer according to claim 1 wherein x is selected from 45-55%, y is selected from 15-25%, z is selected from 5-15%, and w is selected from 5-15%.
3. A polymer for use in a photoresist topcoat layer as claimed in claim 1 wherein the molecular weight of the polymer is selected from 8000-25000da and the pdi is selected from 1.5-2.5.
4. A process for the preparation of a polymer for photoresist topcoat layers according to any one of claims 1 to 3, characterized in that said process comprises: dissolving a monomer and a free radical initiator in an electronic grade solvent to obtain a mixed solution, dripping the mixed solution into the electronic grade solvent under the atmosphere of inert gas to form a reaction system, controlling the reaction temperature and the reaction time, and obtaining a polymer solution after the reaction is finished;
the monomer comprises a monomer A, a monomer B, a monomer C and a monomer D; the monomer A is 4, 4-trifluoro-3-hydroxy-1- (2-methylpropyl) -3- (trifluoromethyl) butyl-2-methyl-2-acrylic acid, and the monomer B is 2- [ [ (trifluoromethyl) sulfonyl ] amino ] ethyl-2-methyl-2-acrylic acid; the monomer C is methacrylic acid-1, 2-tetramethyl propyl ester; the monomer D is trifluoroethyl methacrylate.
5. The method of preparing a polymer for a photoresist topcoat layer according to claim 4 wherein the free radical initiator is any one of benzoyl peroxide, azobisisobutyronitrile, t-butyl benzoyl peroxide, dimethyl azobisisobutyrate, azobisisovaleronitrile, azobisisoheptonitrile.
6. The method of claim 4, wherein the electron-grade solvent is any one of methyl 2-hydroxyisobutyrate, propylene glycol methyl ether, methyl isobutyl carbinol, propylene glycol monomethyl ether acetate, dipropylene glycol methyl ether.
7. The method of preparing a polymer for a photoresist topcoat layer according to claim 4 wherein the free radical initiator is used in an amount of 1 to 10% of the total mass of the monomers; the mass concentration of the monomer and the free radical initiator in the mixed solution is 40-80%, and the mass concentration of the monomer and the free radical initiator in the reaction system is 15-55%.
8. The method of claim 4, wherein the reaction temperature is 55-130 ℃ and the reaction time is 1-12 hours.
9. The method of claim 8, wherein the reaction temperature is 70-100 ℃ and the reaction time is 4-8 hours.
10. Use of a polymer for photoresist top coating, characterized in that the polymer according to any of claims 1-3 or the polymer prepared by the preparation method according to any of claims 4-9 is applied for 193nm immersion photoresist top coating.
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| CN114153124A (en) * | 2021-12-29 | 2022-03-08 | 中节能万润股份有限公司 | Composition for top coating of ArF immersion photoresist and preparation method thereof |
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