CN114395068B - BARC resin for 193nm deep ultraviolet photoresist with narrow distribution and preparation method thereof - Google Patents
BARC resin for 193nm deep ultraviolet photoresist with narrow distribution and preparation method thereof Download PDFInfo
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- CN114395068B CN114395068B CN202111622198.3A CN202111622198A CN114395068B CN 114395068 B CN114395068 B CN 114395068B CN 202111622198 A CN202111622198 A CN 202111622198A CN 114395068 B CN114395068 B CN 114395068B
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- 239000011347 resin Substances 0.000 title claims abstract description 69
- 229920005989 resin Polymers 0.000 title claims abstract description 69
- 229920002120 photoresistant polymer Polymers 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000002904 solvent Substances 0.000 claims abstract description 48
- 239000000178 monomer Substances 0.000 claims abstract description 38
- 239000003999 initiator Substances 0.000 claims abstract description 31
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910003472 fullerene Inorganic materials 0.000 claims abstract description 28
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims abstract description 27
- FUGYGGDSWSUORM-UHFFFAOYSA-N 4-hydroxystyrene Chemical compound OC1=CC=C(C=C)C=C1 FUGYGGDSWSUORM-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000010526 radical polymerization reaction Methods 0.000 claims abstract description 16
- 238000011282 treatment Methods 0.000 claims abstract description 16
- 238000001816 cooling Methods 0.000 claims abstract description 15
- 238000001556 precipitation Methods 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 14
- 238000000926 separation method Methods 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 50
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 48
- 239000012295 chemical reaction liquid Substances 0.000 claims description 38
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- 238000003756 stirring Methods 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 26
- 238000009835 boiling Methods 0.000 claims description 26
- 229910052757 nitrogen Inorganic materials 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000000126 substance Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- 238000005303 weighing Methods 0.000 claims description 13
- 238000009833 condensation Methods 0.000 claims description 12
- 230000005494 condensation Effects 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- 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 9
- 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 2
- 239000000463 material Substances 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 abstract description 13
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 238000011161 development Methods 0.000 abstract description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 4
- 238000012546 transfer Methods 0.000 abstract description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 2
- 239000012046 mixed solvent Substances 0.000 abstract 2
- 239000002244 precipitate Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 7
- 230000035484 reaction time Effects 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 4
- 150000003384 small molecules Chemical class 0.000 description 4
- 239000006117 anti-reflective coating Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000031700 light absorption Effects 0.000 description 3
- 230000008033 biological extinction Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000003670 easy-to-clean Effects 0.000 description 1
- 230000006355 external stress Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000000247 postprecipitation Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012360 testing method Methods 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
- C08F212/00—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 an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
- C08F212/22—Oxygen
- C08F212/24—Phenols or alcohols
-
- 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
- C08F212/00—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 an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
-
- 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
- G03F7/004—Photosensitive materials
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Emergency Medicine (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Polymerisation Methods In General (AREA)
- Materials For Photolithography (AREA)
Abstract
The invention is suitable for the technical field of high polymers, and provides a preparation method of a BARC resin for 193nm deep ultraviolet photoresist with narrow distribution, which comprises the following steps: and (3) dissolving the BARC resin monomer, the carboxylated fullerene and the initiator in a solvent to obtain a monomer solution, heating at a high temperature, performing free radical polymerization reaction to obtain a reaction solution, cooling, and performing precipitation treatment, separation and drying on the cooled reaction solution by using mixed solvents with different polarities to obtain the BARC resin for the photoresist. The carboxyl of the carboxylated fullerene can react with hydroxy of hydroxypropyl methacrylate and p-hydroxystyrene, so that some chain transfer development is reduced; the hollow sphere network structure of the fullerene can reduce light reflection; the molecular weight and molecular weight distribution of the BARC resin can be changed by treating the precipitate with mixed solvents of different polarities, thereby preparing the BARC resin for 193nm deep ultraviolet photoresist with narrow distribution.
Description
Technical Field
The invention belongs to the technical field of polymers, and particularly relates to a BARC resin for 193nm deep ultraviolet photoresist with narrow distribution and a preparation method thereof.
Background
In integrated circuit micropatterning, as the dimensions become smaller, further improvements in photoresist resolution are needed. However, as the exposure wavelength of the photoresist technology is continuously reduced, the resolution is continuously improved as the film is thinner, but the critical dimension cannot be controlled due to the standing wave effect, so that the etching precision is increased. In this regard, the concept of BARC, i.e., bottom anti-reflective coating, also polymeric, is introduced, and a layer of BARC is applied prior to photoresist application, which serves to absorb the incident light and alter the path of the incident light, i.e., k, n, to eliminate standing wave effects.
The BARC resin is also used as a polymer, the molecular weight and the molecular weight distribution of the BARC resin need to be regulated and controlled, in the polymerization process, a free radical polymerization reaction is usually adopted, an initiator is added for regulation and control, but when the reaction is carried out, due to the fact that the reaction contains hydroxyl, some chain transfer development is caused, polymerization is unstable and is not well controlled, and the polymer with narrow distribution cannot be obtained.
Chinese patent publication No. CN112680052a discloses an antireflective coating composition that strongly absorbs 100 to 300nm radiation by using the extinction resin of the present invention, has a high light absorption property, especially at 248nm, and an extinction coefficient K of 0.4 or more or 0.5 or more, thus allowing the use of thinner coating layers and shorter etching times, and the resulting antireflective coating material is easy to clean, and is particularly suitable for use in thin layer photoresists to obtain high resolution lithographic patterns, but the molecular weight of the resin polymer is not narrowly distributed and is not easily processable, and thus research of BARC resins for 193nm deep ultraviolet photoresists of narrow distribution is urgently required.
Disclosure of Invention
The embodiment of the invention provides a BARC resin for 193nm deep ultraviolet photoresist with narrow distribution and a preparation method thereof, aiming at solving the technical problem that the molecular weight of the BARC resin for 193nm deep ultraviolet photoresist in the prior art does not have narrow distribution.
A method for preparing a BARC resin for a narrow-distribution 193nm deep ultraviolet photoresist, which is characterized by comprising the following steps:
s1, placing p-hydroxystyrene, styrene and hydroxypropyl methacrylate into a four-neck flask containing a solvent, and stirring until monomers are uniformly mixed;
s2, after the monomer is dissolved, adding the hollow net-shaped substance and the initiator, and stirring until the hollow net-shaped substance and the initiator are dissolved;
s3, placing the four-neck flask with the reaction liquid in an oil bath pot with a magnetic stirrer, installing a condensation pipe and a nitrogen interface, starting condensed water, introducing nitrogen, starting stirring, heating to the boiling point temperature of the solvent, recording the temperature and carrying out free radical polymerization after the boiling phenomenon occurs;
s4, cooling the reaction liquid, and carrying out precipitation treatment on the reaction liquid by using solvents with different polarities;
s5, solid-liquid separation, drying and weighing to obtain the BARC resin for the 193nm deep ultraviolet photoresist with narrow distribution.
Further, in the preparation method of the BARC resin for 193nm deep ultraviolet photoresist with narrow distribution, the solvent in the step S1 is tetrahydrofuran.
Further, in the preparation method of the BARC resin for the 193nm deep ultraviolet photoresist with narrow distribution, the dosage ratio of the p-hydroxystyrene, the styrene, the hydroxypropyl methacrylate and the tetrahydrofuran solvent in the step S1 is 1-10:1-10:1-10:12-120.
Further, in the preparation method of the BARC resin for 193nm deep ultraviolet photoresist with narrow distribution, the hollow sphere network substance in the step S2 is carboxylated fullerene.
Further, in the preparation method of the BARC resin for 193nm deep ultraviolet photoresist with narrow distribution, the initiator in the step S2 is one or more of azobisisobutyronitrile, azobisisovaleronitrile and azobisisoheptonitrile.
Furthermore, in the preparation method of the BARC resin for the 193nm deep ultraviolet photoresist with narrow distribution, the dosage ratio of the carboxylated fullerene to the initiator in the step S2 is 13-130:0.06-0.6.
Further, in the preparation method of the BARC resin for 193nm deep ultraviolet photoresist with narrow distribution, the boiling point temperature of the solvent in the step S3 is 65-66 ℃.
Further, in the preparation method of the BARC resin for 193nm deep ultraviolet photoresist with narrow distribution, the time of the radical polymerization reaction in the step S3 is 18-20 hours.
Further, in the preparation method of the BARC resin for 193nm deep ultraviolet photoresist with narrow distribution, the solvents with different polarities in the step S4 are methanol/water= (0-10)/(10-0), ethanol/water= (0-10)/(10-0), and so on.
Advantageous effects
(1) The invention provides a BARC resin for 193nm deep ultraviolet photoresist with narrow distribution and a preparation method thereof, wherein the method comprises the following steps: and (3) placing the BARC resin monomer for 193nm deep ultraviolet photoresist and the initiator into a solvent for dissolution, placing the monomer solution into a nitrogen environment for high-temperature heating, performing polymerization reaction, obtaining a cooling reaction liquid after the reaction is finished, and performing precipitation, separation and drying treatment on the cooling reaction liquid by using solvents with different polarities to obtain the BARC resin for 193nm deep ultraviolet photoresist with narrow distribution.
(2) The invention provides a BARC resin for 193nm deep ultraviolet photoresist with narrow distribution and a preparation method thereof, wherein carboxyl of carboxylated fullerene can react with hydroxy of hydroxypropyl methacrylate and p-hydroxystyrene, some chain transfer development is avoided, polymerization instability is avoided, the reaction is well controlled, a polymer with narrow distribution can be obtained, and meanwhile, the light reflection can be reduced by a hollow sphere network structure of fullerene, so that the light absorption performance of the BARC resin is more stable.
(3) In the process of preparing the BARC resin for the 193nm deep ultraviolet photoresist, the BARC resin for the 193nm deep ultraviolet photoresist is subjected to aftertreatment, short-chain polymers are directly removed by utilizing the polarity relation of solvents, and long-chain polymers are reserved, so that the narrow-distribution polymers are obtained, the narrow-distribution polymers are uniform in particles, relatively consistent in reaction to external stress, reduced in breaking rate, more stable in light absorption performance and easy to process, and the standing wave effect can be better eliminated and can be applied to 193nm deep ultraviolet photoresist technology.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Example 1
A preparation method of a BARC resin for a 193nm deep ultraviolet photoresist with narrow distribution comprises the following steps:
the mass ratio is as follows: the dosage ratio of the p-hydroxystyrene, the styrene, the hydroxypropyl methacrylate and the tetrahydrofuran solvent is 1:1:1:12, and the dosage ratio of the carboxylated fullerene and the initiator is 13:0.06.
S1, placing p-hydroxystyrene, styrene and hydroxypropyl methacrylate into a four-neck flask containing tetrahydrofuran solvent, and stirring until the monomers are uniformly mixed;
s2, after the monomer is dissolved, adding the carboxylated fullerene of the hollow net-shaped substance and the azo diisobutyronitrile serving as an initiator, and stirring until the monomer is dissolved;
s3, placing the four-neck flask with the reaction liquid in an oil bath pot with a magnetic stirrer, installing a condensation pipe and a nitrogen interface, starting condensed water, introducing nitrogen, starting stirring, raising the temperature to 65 ℃ of the boiling point of the solvent, recording the temperature and carrying out free radical polymerization reaction after the boiling phenomenon occurs, wherein the reaction time is 18 hours;
s4, cooling the reaction liquid, and carrying out precipitation treatment on the reaction liquid by using solvents with different polarities, wherein the solvents with different polarities are methanol/water=9/1;
s5, solid-liquid separation, drying and weighing to obtain the BARC resin for the 193nm deep ultraviolet photoresist with narrow distribution.
Example 2
A preparation method of a BARC resin for a 193nm deep ultraviolet photoresist with narrow distribution comprises the following steps:
the mass ratio is as follows: the dosage ratio of the p-hydroxystyrene, the styrene, the hydroxypropyl methacrylate and the tetrahydrofuran solvent is 2:1-10:2:20, and the dosage ratio of the carboxylated fullerene and the initiator is 20:0.1.
S1, placing p-hydroxystyrene, styrene and hydroxypropyl methacrylate into a four-neck flask containing tetrahydrofuran solvent, and stirring until the monomers are uniformly mixed;
s2, after the monomer is dissolved, adding the carboxylated fullerene of the hollow net-shaped substance and the azo diisovaleronitrile serving as an initiator, and stirring until the monomer is dissolved;
s3, placing the four-neck flask with the reaction liquid in an oil bath pot with a magnetic stirrer, installing a condensation pipe and a nitrogen interface, starting condensed water, introducing nitrogen, starting stirring, raising the temperature to 65.2 ℃ of the boiling point of the solvent, recording the temperature and carrying out free radical polymerization reaction for 18.2 hours after the boiling phenomenon occurs;
s4, cooling the reaction liquid, and carrying out precipitation treatment on the reaction liquid by using solvents with different polarities, wherein the solvents with different polarities are methanol/water=5/5;
s5, solid-liquid separation, drying and weighing to obtain the BARC resin for the 193nm deep ultraviolet photoresist with narrow distribution.
Example 3
A preparation method of a BARC resin for a 193nm deep ultraviolet photoresist with narrow distribution comprises the following steps:
the mass ratio is as follows: the dosage ratio of the p-hydroxystyrene, the styrene, the hydroxypropyl methacrylate and the tetrahydrofuran solvent is 3:3:4:30, and the dosage ratio of the carboxylated fullerene and the initiator is 30:0.2.
S1, placing p-hydroxystyrene, styrene and hydroxypropyl methacrylate into a four-neck flask containing tetrahydrofuran solvent, and stirring until the monomers are uniformly mixed;
s2, after the monomer is dissolved, adding the carboxylated fullerene serving as a hollow net-shaped substance and azo-diisoheptonitrile serving as an initiator, and stirring until the monomer is dissolved;
s3, placing the four-neck flask with the reaction liquid in an oil bath pot with a magnetic stirrer, installing a condensation pipe and a nitrogen interface, starting condensed water, introducing nitrogen, starting stirring, raising the temperature to 65.4 ℃ of the boiling point of the solvent, recording the temperature and carrying out free radical polymerization reaction after the boiling phenomenon occurs, wherein the reaction time is 18.4 hours;
s4, cooling the reaction liquid, and carrying out precipitation treatment on the reaction liquid by using solvents with different polarities, wherein the solvents with different polarities are methanol/water=1/9;
s5, solid-liquid separation, drying and weighing to obtain the BARC resin for the 193nm deep ultraviolet photoresist with narrow distribution.
Example 4
A preparation method of a BARC resin for a 193nm deep ultraviolet photoresist with narrow distribution comprises the following steps:
the mass ratio is as follows: the dosage ratio of the p-hydroxystyrene, the styrene, the hydroxypropyl methacrylate and the tetrahydrofuran solvent is 4:4:4:40, and the dosage ratio of the carboxylated fullerene and the initiator is 40:0.4.
S1, placing p-hydroxystyrene, styrene and hydroxypropyl methacrylate into a four-neck flask containing tetrahydrofuran solvent, and stirring until the monomers are uniformly mixed;
s2, after the monomer is dissolved, adding the carboxylated fullerene serving as a hollow net-shaped substance and azo-diisoheptonitrile serving as an initiator, and stirring until the monomer is dissolved;
s3, placing the four-neck flask with the reaction liquid in an oil bath pot with a magnetic stirrer, installing a condensation pipe and a nitrogen interface, starting condensed water, introducing nitrogen, starting stirring, raising the temperature to 65.5 ℃ of the boiling point of the solvent, recording the temperature and carrying out free radical polymerization reaction for 18.5 hours after the boiling phenomenon occurs;
s4, cooling the reaction liquid, and carrying out precipitation treatment on the reaction liquid by using solvents with different polarities, wherein the solvents with different polarities are ethanol/water=9/1;
s5, solid-liquid separation, drying and weighing to obtain the BARC resin for the 193nm deep ultraviolet photoresist with narrow distribution.
Example 5
A preparation method of a BARC resin for a 193nm deep ultraviolet photoresist with narrow distribution comprises the following steps:
the mass ratio is as follows: the dosage ratio of the p-hydroxystyrene, the styrene, the hydroxypropyl methacrylate and the tetrahydrofuran solvent is 5:5:5:56, and the dosage ratio of the carboxylated fullerene and the initiator is 50:0.051.
S1, placing p-hydroxystyrene, styrene and hydroxypropyl methacrylate into a four-neck flask containing tetrahydrofuran solvent, and stirring until the monomers are uniformly mixed;
s2, after the monomer is dissolved, adding the carboxylated fullerene serving as a hollow net-shaped substance and azo-diisoheptonitrile serving as an initiator, and stirring until the monomer is dissolved;
s3, placing the four-neck flask with the reaction liquid in an oil bath pot with a magnetic stirrer, installing a condensation pipe and a nitrogen interface, starting condensed water, introducing nitrogen, starting stirring, raising the temperature to 65.6 ℃ of the boiling point of the solvent, recording the temperature and carrying out free radical polymerization reaction for 18.6 hours after the boiling phenomenon occurs;
s4, cooling the reaction liquid, and carrying out precipitation treatment on the reaction liquid by using solvents with different polarities, wherein the solvents with different polarities are ethanol/water=5/5;
s5, solid-liquid separation, drying and weighing to obtain the BARC resin for the 193nm deep ultraviolet photoresist with narrow distribution.
Example 6
A preparation method of a BARC resin for a 193nm deep ultraviolet photoresist with narrow distribution comprises the following steps:
the mass ratio is as follows: the dosage ratio of the p-hydroxystyrene, the styrene, the hydroxypropyl methacrylate and the tetrahydrofuran solvent is 10:10:10:120, and the dosage ratio of the carboxylated fullerene and the initiator is 130:0.6.
S1, placing p-hydroxystyrene, styrene and hydroxypropyl methacrylate into a four-neck flask containing tetrahydrofuran solvent, and stirring until the monomers are uniformly mixed;
s2, after the monomer is dissolved, adding the carboxylated fullerene serving as a hollow net-shaped substance and azo-diisoheptonitrile serving as an initiator, and stirring until the monomer is dissolved;
s3, placing the four-neck flask with the reaction liquid in an oil bath pot with a magnetic stirrer, installing a condensation pipe and a nitrogen interface, starting condensed water, introducing nitrogen, starting stirring, heating to the boiling point temperature of a solvent to 66 ℃, recording the temperature and carrying out free radical polymerization reaction after the boiling phenomenon occurs, wherein the reaction time is 20 hours;
s4, cooling the reaction liquid, and carrying out precipitation treatment on the reaction liquid by using solvents with different polarities, wherein the solvents with different polarities are ethanol/water=1/9;
s5, solid-liquid separation, drying and weighing to obtain the BARC resin for the 193nm deep ultraviolet photoresist with narrow distribution.
Comparative example 1
A preparation method of a BARC resin for a 193nm deep ultraviolet photoresist with narrow distribution comprises the following steps:
the mass ratio is as follows: the dosage ratio of the p-hydroxystyrene, the styrene, the hydroxypropyl methacrylate and the tetrahydrofuran solvent is 1:1:1:12, and the dosage ratio of the carboxylated fullerene and the initiator is 13:0.06.
S1, placing p-hydroxystyrene, styrene and hydroxypropyl methacrylate into a four-neck flask containing tetrahydrofuran solvent, and stirring until the monomers are uniformly mixed;
s2, after the monomer is dissolved, adding the carboxylated fullerene of the hollow net-shaped substance and the azo diisobutyronitrile serving as an initiator, and stirring until the monomer is dissolved;
s3, placing the four-neck flask with the reaction liquid in an oil bath pot with a magnetic stirrer, installing a condensation pipe and a nitrogen interface, starting condensed water, introducing nitrogen, starting stirring, raising the temperature to 65 ℃ of the boiling point of the solvent, recording the temperature and carrying out free radical polymerization reaction after the boiling phenomenon occurs, wherein the reaction time is 18 hours;
s4, cooling the reaction liquid, and carrying out precipitation treatment on the reaction liquid by using solvents with different polarities, wherein the solvents with different polarities are methanol/water=0/10;
s5, solid-liquid separation, drying and weighing to obtain the BARC resin for the 193nm deep ultraviolet photoresist with narrow distribution.
Comparative example 2
A preparation method of a BARC resin for a 193nm deep ultraviolet photoresist with narrow distribution comprises the following steps:
the mass ratio is as follows: the dosage ratio of the p-hydroxystyrene, the styrene, the hydroxypropyl methacrylate and the tetrahydrofuran solvent is 1:1:1:12, and the dosage ratio of the carboxylated fullerene and the initiator is 13:0.06.
S1, placing p-hydroxystyrene, styrene and hydroxypropyl methacrylate into a four-neck flask containing tetrahydrofuran solvent, and stirring until the monomers are uniformly mixed;
s2, after the monomer is dissolved, adding the carboxylated fullerene of the hollow net-shaped substance and the azo diisobutyronitrile serving as an initiator, and stirring until the monomer is dissolved;
s3, placing the four-neck flask with the reaction liquid in an oil bath pot with a magnetic stirrer, installing a condensation pipe and a nitrogen interface, starting condensed water, introducing nitrogen, starting stirring, raising the temperature to 65 ℃ of the boiling point of the solvent, recording the temperature and carrying out free radical polymerization reaction after the boiling phenomenon occurs, wherein the reaction time is 18 hours;
s4, cooling the reaction liquid, and carrying out precipitation treatment on the reaction liquid by using solvents with different polarities, wherein the solvents with different polarities are ethanol/water=10/0;
s5, solid-liquid separation, drying and weighing to obtain the BARC resin for the 193nm deep ultraviolet photoresist with narrow distribution.
Comparative example 3
A preparation method of a BARC resin for a 193nm deep ultraviolet photoresist with narrow distribution comprises the following steps:
the mass ratio is as follows: the dosage ratio of the p-hydroxystyrene, the styrene, the hydroxypropyl methacrylate and the tetrahydrofuran solvent is 1:1:1:12, and the dosage ratio of the carboxylated fullerene and the initiator is 13:0.06.
S1, placing p-hydroxystyrene, styrene and hydroxypropyl methacrylate into a four-neck flask containing tetrahydrofuran solvent, and stirring until the monomers are uniformly mixed;
s2, after the monomer is dissolved, adding the carboxylated fullerene of the hollow net-shaped substance and the azo diisobutyronitrile serving as an initiator, and stirring until the monomer is dissolved;
s3, placing the four-neck flask with the reaction liquid in an oil bath pot with a magnetic stirrer, installing a condensation pipe and a nitrogen interface, starting condensed water, introducing nitrogen, starting stirring, raising the temperature to 65 ℃ of the boiling point of the solvent, recording the temperature and carrying out free radical polymerization reaction after the boiling phenomenon occurs, wherein the reaction time is 18 hours;
s4, cooling the reaction liquid, and carrying out precipitation treatment on the reaction liquid by using solvents with different polarities, wherein the solvents with different polarities are methanol/water=10/0;
s5, solid-liquid separation, drying and weighing to obtain the BARC resin for the 193nm deep ultraviolet photoresist with narrow distribution.
Comparative example 4
A preparation method of a BARC resin for a 193nm deep ultraviolet photoresist with narrow distribution comprises the following steps:
the mass ratio is as follows: the dosage ratio of the p-hydroxystyrene, the styrene, the hydroxypropyl methacrylate and the tetrahydrofuran solvent is 1:1:1:12, and the dosage of the initiator is 0.06g.
S1, placing p-hydroxystyrene, styrene and hydroxypropyl methacrylate into a four-neck flask containing tetrahydrofuran solvent, and stirring until the monomers are uniformly mixed;
s2, after the monomer is dissolved, adding an initiator azodiisobutyronitrile, and stirring until the monomer is dissolved;
s3, placing the four-neck flask with the reaction liquid in an oil bath pot with a magnetic stirrer, installing a condensation pipe and a nitrogen interface, starting condensed water, introducing nitrogen, starting stirring, raising the temperature to 65 ℃ of the boiling point of the solvent, recording the temperature and carrying out free radical polymerization reaction after the boiling phenomenon occurs, wherein the reaction time is 18 hours;
s4, cooling the reaction liquid, and carrying out precipitation treatment on the reaction liquid by using solvents with different polarities, wherein the solvents with different polarities are methanol/water=9/1;
s5, solid-liquid separation, drying and weighing to obtain the BARC resin for the 193nm deep ultraviolet photoresist with narrow distribution.
GPC was measured after weighing the BARC resin for 193nm deep ultraviolet photoresist of narrow distribution, and the BARC resin for 193nm deep ultraviolet photoresist of narrow distribution prepared in examples 1 to 6 and comparative examples 1 to 4 was calculated to measure yield, weight average molecular weight and PDI, and the test results are shown in Table 1:
TABLE 1 polymerization results
According to the results shown in Table 1, the results of resins treated with different polarities are different from the comparative examples, and the resins of the present invention have the highest yield in water with the strongest polarity, and small molecules are not removed, resulting in a broader molecular weight distribution and a low molecular weight. When treated with methanol having weak polarity, small molecules are removed and the molecular weight distribution becomes narrow. And further increases the polarity of the precipitant, such as ethanol. The molecular weight distribution is further narrowed. However, since too many small molecules are removed, the final yield is low and the molecular weight becomes large. The hydroxyl groups of hydroxypropyl methacrylate and p-hydroxystyrene, which were not added with the carboxylated fullerene of the hollow net-like substance in comparative example 4, caused some chain transfer development, resulted in unstable polymerization, and could not give a narrow distribution of polymer.
In the examples, it was also concluded that by precipitation treatment with both methanol/water and ethanol/water systems, small molecules can be effectively removed and molecular weight distribution reduced without the yield becoming too low when water is combined with less polar methanol. When an ethanol/water system is used, the polarity change is too large, and long chains are removed at the same time when the small chain polymer is removed, so that the yield of the resin treated by the final subsystem is low, the molecular weight is large, and the molecular weight distribution is narrow and uniform.
In summary, the method of post-precipitation treatment by using different solvents to adjust the polarity can indeed change the molecular weight and molecular weight distribution of the resin, and can adjust the change of the polarity to float according to the requirement, thereby achieving the desired polymer.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (9)
1. A method for preparing a BARC resin for a narrow-distribution 193nm deep ultraviolet photoresist, which is characterized by comprising the following steps:
s1, placing p-hydroxystyrene, styrene and hydroxypropyl methacrylate into a four-neck flask containing a solvent, and stirring until monomers are uniformly mixed;
s2, after the monomer is dissolved, adding the hollow net-shaped substance and the initiator, and stirring until the hollow net-shaped substance and the initiator are dissolved;
s3, placing the four-neck flask with the reaction liquid in an oil bath pot with a magnetic stirrer, installing a condensation pipe and a nitrogen interface, starting condensed water, introducing nitrogen, starting stirring, heating to the boiling point temperature of the solvent, recording the temperature and carrying out free radical polymerization after the boiling phenomenon occurs;
s4, cooling the reaction liquid, and carrying out precipitation treatment on the reaction liquid by using solvents with different polarities;
s5, solid-liquid separation, drying and weighing to obtain the BARC resin for the 193nm deep ultraviolet photoresist with narrow distribution;
wherein, in the step S4, the solvents with different polarities are methanol/water= (0-10)/(10-0) or ethanol/water= (0-10)/(10-0), and meanwhile, the solvents with different polarities are not pure water or pure ethanol or pure methanol.
2. The method for preparing BARC resin for 193nm deep ultraviolet photoresist according to claim 1, wherein the solvent in the step S1 is tetrahydrofuran.
3. The method for preparing BARC resin for 193nm deep ultraviolet photoresist according to claim 1, wherein the dosage ratio of the p-hydroxystyrene, styrene, hydroxypropyl methacrylate and tetrahydrofuran solvent in the step S1 is 1-10:1-10:1-10:12-120.
4. The method for preparing BARC resin for 193nm deep ultraviolet photoresist according to claim 2, wherein the hollow sphere network material in step S2 is carboxylated fullerene.
5. The method for preparing BARC resin for 193nm deep ultraviolet photoresist with narrow distribution according to claim 2, wherein the dosage ratio of carboxylated fullerene and initiator in the step S2 is 13-130:0.06-0.6.
6. The method for preparing BARC resin for 193nm deep ultraviolet photoresist according to claim 2, wherein the initiator in the step S2 is one or more of azobisisobutyronitrile, azobisisovaleronitrile, and azobisisoheptonitrile.
7. The method for preparing a BARC resin for a narrow profile 193nm deep ultraviolet photoresist according to claim 1, wherein the boiling temperature of the solvent in the step S3 is 65-66 ℃.
8. The method for preparing a BARC resin for a narrow profile 193nm deep ultraviolet photoresist according to claim 1, wherein the time of the radical polymerization in the step S3 is 18 to 20 hours.
9. A BARC resin for a narrow distribution 193nm deep ultraviolet photoresist, characterized in that it is prepared by the preparation method of the BARC resin for a narrow distribution 193nm deep ultraviolet photoresist according to any one of claims 1 to 8.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08239209A (en) * | 1995-03-01 | 1996-09-17 | Toyota Central Res & Dev Lab Inc | Bonded substance of fullerene and unsaturated compound and its production |
| CN1373143A (en) * | 2001-03-07 | 2002-10-09 | 海力士半导体有限公司 | Organic antireflective coating polymer, antireflective paint composition contg. said polymer, and process for preparing same |
| JP2005241963A (en) * | 2004-02-26 | 2005-09-08 | Jsr Corp | Composition for forming antireflection film and antireflection film |
| CN104919370A (en) * | 2012-12-13 | 2015-09-16 | Az电子材料（卢森堡）有限公司 | Composition for forming overlay film, and resist pattern formation method using same |
| CN109426100A (en) * | 2018-10-29 | 2019-03-05 | 福建泓光半导体材料有限公司 | A kind of photoresist of etch resistant and its preparation method and application and photolithography method |
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| JP5395012B2 (en) * | 2010-08-23 | 2014-01-22 | 信越化学工業株式会社 | Resist underlayer film material, resist underlayer film forming method, pattern forming method, fullerene derivative |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08239209A (en) * | 1995-03-01 | 1996-09-17 | Toyota Central Res & Dev Lab Inc | Bonded substance of fullerene and unsaturated compound and its production |
| CN1373143A (en) * | 2001-03-07 | 2002-10-09 | 海力士半导体有限公司 | Organic antireflective coating polymer, antireflective paint composition contg. said polymer, and process for preparing same |
| JP2005241963A (en) * | 2004-02-26 | 2005-09-08 | Jsr Corp | Composition for forming antireflection film and antireflection film |
| CN104919370A (en) * | 2012-12-13 | 2015-09-16 | Az电子材料（卢森堡）有限公司 | Composition for forming overlay film, and resist pattern formation method using same |
| CN109426100A (en) * | 2018-10-29 | 2019-03-05 | 福建泓光半导体材料有限公司 | A kind of photoresist of etch resistant and its preparation method and application and photolithography method |
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