CN116693755B - ArF photoresist film-forming polymer, preparation method thereof, photoresist prepared from polymer and application of polymer - Google Patents

ArF photoresist film-forming polymer, preparation method thereof, photoresist prepared from polymer and application of polymer Download PDF

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CN116693755B
CN116693755B CN202310759537.5A CN202310759537A CN116693755B CN 116693755 B CN116693755 B CN 116693755B CN 202310759537 A CN202310759537 A CN 202310759537A CN 116693755 B CN116693755 B CN 116693755B
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photoresist film
forming polymer
monomer
polymer
arf photoresist
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CN116693755A (en
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郑祥飞
徐亮
陈韦帆
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Ruihong Suzhou Electronic Chemicals Co ltd
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Ruihong Suzhou Electronic Chemicals Co ltd
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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
    • C08F222/00—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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/04—Anhydrides, e.g. cyclic anhydrides
    • C08F222/06—Maleic anhydride
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups

Abstract

The application relates to the technical field of photoresist, and particularly discloses an ArF photoresist film-forming polymer, a preparation method thereof, photoresist prepared from the polymer and application thereof. An ArF photoresist film-forming polymer comprising the following components in proportion: 5-20mol% of norbornene new monomer; 45-55mol% of maleic anhydride monomer; the side chain of the norbornene monomer contains 20-40mol% of protecting group. The preparation method of the ArF photoresist film-forming polymer comprises the following steps: dissolving, heating for reaction, purifying, drying and the like. The photoresist comprises the following components: arF photoresist film forming polymer, photoacid generator, alkaline additive, and third solvent. The photoresist has good adhesiveness and etching resistance.

Description

ArF photoresist film-forming polymer, preparation method thereof, photoresist prepared from polymer and application of polymer
Technical Field
The application relates to the technical field of photoresist, in particular to an ArF photoresist film-forming polymer, a preparation method thereof, photoresist prepared from the polymer and application thereof.
Background
With the continuous increase of integrated circuit integration, the device is required to be smaller and smaller, and the resolution of photoresist is developed from micron and submicron to nanometer, which requires the wavelength of the exposure light source to be reduced continuously. ArF exposure is divided into dry lithography and immersion lithography, and combines multiple exposure techniques, with resolution coverage of 90-7nm, and is the dominant process for chip fabrication. ArF photoresists require high light transmittance (at 193nm wavelength), high resolution, fast sensitivity, high etch resistance, low edge roughness, and few defects, and therefore, place higher demands on film forming polymers.
Generally, the low absorption of the photoresist at 193nm wavelength can be satisfied by introducing a large amount of alicyclic structures into the ArF photoresist film-forming polymer structure, and the photoresist has strong etching resistance, but can cause the reduced adhesion between the photoresist and the substrate; in addition, the cyclic structures of cycloolefin and norbornene monomer main chains are introduced into the ArF photoresist film-forming polymer structure, so that the light transmittance and the etching resistance of the film are greatly improved, but the film is too strong in hydrophobicity and poor in adhesive force, and the prepared film is large in brittleness.
In view of this, it is necessary to develop an ArF photoresist having good etching resistance and high adhesion.
Disclosure of Invention
In order to improve the etching resistance and the adhesive force of the ArF photoresist, the application provides an ArF photoresist film-forming polymer, a preparation method thereof, a photoresist prepared from the polymer and application thereof.
The ArF photoresist film-forming polymer provided by the application adopts the following technical scheme:
in a first aspect, the present application provides an ArF photoresist film-forming polymer, which adopts the following technical scheme:
an ArF photoresist film-forming polymer comprises the following components in proportion:
5-20mol% of norbornene new monomer;
45-55mol% of maleic anhydride monomer;
20-40mol% of norbornene monomer with side chain containing protecting group;
the new norbornene monomer has the following structural formula:
wherein R1 is an alkyl chain, X is an alkyl group containing a hydroxyl group and a nitrile group, and Y is a methylene group or an oxygen atom.
By adopting the technical scheme, the norbornene monomer and the maleic anhydride monomer form a maleic anhydride-norbornene polymer through free radical polymerization, and the ArF photoresist prepared by taking the polymer as matrix resin has excellent etching resistance and adhesive force. The maleic anhydride and the norbornene carbon-carbon double bond participate in free radical polymerization, and the cyclic structure of the maleic anhydride and the norbornene carbon-carbon double bond is introduced into a polymer main chain, so that the heat resistance and the etching resistance of the photoresist are improved; the flexible alkyl chain and polar group of the side chain of the norbornene new monomer improves the brittleness and adhesion of the polymer.
In a specific embodiment, the norbornene novel monomer is obtained by reacting a cyclic diene monomer (a) with an olefin monomer (b) DA (Diels-Alder) as follows:
wherein (a) the monomer is one of cyclopentadiene, furan and 1, 3-cyclohexadiene;
(b) The monomer is N-substituted maleimide monomer, and the structural general formula is as follows:
wherein R is a substituent containing a nitrile group.
Preferably, the structure of the monomer (b) is one of the following structures:
in a specific embodiment, the novel norbornene monomer having a protecting group in the side chain has the following structural formula:
wherein R2, R3 and R3 are alkyl or alicyclic, and R2, R3 and R4 can also form a cyclic structure.
In a second aspect, the present application provides a method for preparing an ArF photoresist film-forming polymer, which adopts the following technical scheme: a method for preparing an ArF photoresist film-forming polymer, comprising the following steps:
s1, dissolving a norbornene new monomer, a maleic anhydride monomer, a norbornene new monomer with a side chain containing a protecting group and an initiator in a first solvent to obtain a solution A; the solution A is treated by a method of N 2 Heating to 60-90 ℃ for reaction for 8-20h under the protection to obtain a polymer solution;
s2, dropwise adding the polymer solution into a second solvent, and performing suction filtration to obtain a white precipitate;
s3, dissolving the white precipitate in a first solvent to obtain a polymer solution;
s4, repeating the steps S2 and S3 1-2 times, and drying after suction filtration to obtain purified white copolymer powder.
By adopting the technical scheme, the ArF photoresist film-forming polymer with good adhesiveness and etching resistance can be prepared by a simple process without complex preparation conditions.
Preferably, the first solvent is one of tetrahydrofuran, butanone, butyl acetate and propylene glycol methyl ether acetate; the second solvent is one of petroleum ether, n-hexane, n-heptane and alcohols.
In a third aspect, the present application provides a photoresist made of an ArF photoresist film-forming polymer, which adopts the following technical scheme:
the photoresist prepared from the ArF photoresist film-forming polymer comprises the following components:
an ArF photoresist film forming polymer;
a photoacid generator;
an alkaline additive;
a third solvent;
the weight ratio of the photoacid generator to the ArF photoresist film-forming polymer is (0.5-10): 100;
the weight ratio of the alkaline additive to the ArF photoresist film-forming polymer is (0.05-1): 100;
the weight ratio of the third solvent to the ArF photoresist film-forming polymer is 100: (5-15).
In a specific embodiment, the photoacid generator is one or more of diazonium salts, sulfonium salts, iodonium salts, sulfonyl diazomethane, N-hydroxy imide sulfonate, imine sulfonate, nitrobenzyl sulfonate, oxime sulfonate.
Preferably, the photoacid generator is 2- (adamantane-1-carbonyl) oxy) -1, 1-difluoroethanesulfonic acid (4-methylphenyl) diphenylsulfonium salt, diphenyliodonium triflate, diphenyliodonium camphorsulfonate, diphenyliodonium perfluoro-1-butanesulfonate, diphenyliodonium perfluorooctanesulfonate, 4-methoxyphenyl iodonium trifluoromethanesulfonate, bis (4-tert-butylphenyl) iodonium triflate, bis (4-tert-butylphenyl) iodonium perfluoro-1-butanesulfonate, bis (4-tert-butylphenyl) iodonium camphor sulfonate, bis (4-tert-butylphenyl) iodonium perfluorooctanesulfonate, triphenylsulfonium triflate, triphenylsulfonium camphor sulfonate, triphenylsulfonium perfluoro-1-butylsulfonate, triphenylsulfonium perfluorooctanesulfonate, 4-methoxyphenyl iodonium trifluoromethanesulfonate, p-methylphenyl diphenylsulfonium triflate, p-tolyl diphenylsulfonium perfluorooctanesulfonate, p-tolyl sulfonium perfluorooctanesulfonate, p-tolyl-1-diphenylsulfonium sulfonate, 4-diphenyl sulfonium triflate, 4-hydroxy-2-trifluoromethanesulfonate, 4-trifluoromethanesulfonate, any one or more of N- (phenylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) succinimide, N- (perfluoro-1-butanesulfonic acid) succinimide, N- (perfluorooctanesulfonic acid) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (perfluorooctanesulfonic acid) phthalimide, N- (trifluoromethylsulfonyloxy) -5-norbornene-2, 3-dicarboxyimide, N- (perfluoro-1-butanesulfonic acid) -5-norbornene-2, 3-dicarboxyimide, N- (perfluorooctanesulfonic acid) -5-norbornene-2, 3-dicarboxyimide, N- (trifluoromethylsulfonyloxy) naphthalimide, N- (perfluoro-1-butanesulfonic acid) naphthalimide, N- (perfluorooctanesulfonic acid) naphthalimide, N- (10-camphorsulfonyloxy) naphthalimide.
By adopting the technical scheme, the photoacid generator selected by the application has good thermal stability and chemical stability, and is beneficial to improving the uniformity of the prepared ArF photoresist film-forming polymer.
In a specific embodiment, the basic additive is one or more of tetra-n-butylammonium hydroxide, tetrabutylammonium acetate, tri-n-octylamine, 2, 6-diisopropylaniline, triethanolamine.
In a specific embodiment, the third solvent is one or more of propylene glycol methyl ether acetate, ethyl lactate, ethyl acetate, 2-heptanone, ethylene glycol monomethyl ether acetate, cyclohexanone, methyl pentanol, 3-ethoxypropionic acid.
In a third aspect, the present application provides a lithographic pattern, which adopts the following technical scheme:
and photoetching patterns, wherein the photoresist prepared from the ArF photoresist film-forming polymer is obtained through the processes of film coating, soft baking, exposure, middle baking and development.
In summary, the present application has the following beneficial effects:
1. the application prepares ArF photoresist by carrying out free radical polymerization on norbornene new monomer and maleic anhydride monomer to form a polymer and taking the polymer as matrix resin; the cyclic structure of the norbornene new monomer is introduced into the main chain of the polymer, so that the etching resistance of the photoresist is improved; the polar substituent and alkyl chain on the side chain of the norbornene new monomer improve the adhesive force and brittleness of the polymer, so that the obtained ArF photoresist has excellent etching resistance and adhesive force;
2. the ArF photoresist film-forming polymer with good adhesiveness and etching resistance can be prepared by a simple process, and complex preparation conditions are not required.
Detailed Description
The present application is further described in detail below in connection with the preparation examples and examples.
Preparation example
Preparation example 1
The invention discloses a preparation method of a norbornene new monomer, which comprises the following specific processes: dissolving 1mol of furan (cas 110-00-9) with chloroform, adding into a single-neck flask with a stirrer, dropwise adding 1mol of substituted olefin (b) monomer, heating to 60 ℃ for reaction for 24 hours, stopping, adding the resultant into ethyl acetate, stirring and purifying, and drying in a vacuum oven for 24 hours, wherein the reaction equation is as follows:
preparation example 2
The invention discloses a preparation method of a norbornene new monomer, which comprises the following specific processes: dissolving 1mol of cyclopentadiene (cas 542-92-7) with chloroform, adding into a single-neck flask with a stirrer, dropwise adding 1mol of substituted olefin (b) monomer, heating to 60 ℃ for reaction for 24 hours, stopping, adding the resultant into ethyl acetate, stirring and purifying, and drying in a vacuum oven for 24 hours, wherein the reaction equation is as follows:
preparation example 3
The preparation is substantially the same as in preparation example 2, except that the substituted olefin (b) monomer has a different structural formula, and the reaction equation is as follows:
examples
Example 1
The present example discloses an ArF photoresist film-forming polymer prepared from 7.64g of norbornene new monomer, 4.9g of maleic anhydride, 2.72g of tert-butyl 5-norbornene-2-carboxylate and 0.82g of azobisisobutyronitrile as raw materials, wherein the norbornene new monomer was prepared by using preparation 1.
The embodiment also discloses a preparation method of the ArF photoresist film-forming polymer, which comprises the following steps:
s1, accurately weighing 7.64g of norbornene new monomer, 4.9g of maleic anhydride, 2.72g of 5-norbornene-2-carboxylic acid tert-butyl ester (cas 154970-45-3) and 0.82g of azodiisobutyronitrile at 25 ℃, and dissolving with 28g of tetrahydrofuran to obtain a solution A;
s2, 20g of tetrahydrofuran was charged into a 100ml four-necked flask equipped with a stirrer, a condenser and a thermometer, followed by N 2 Under the protection action, stirring and heating to about 65 ℃, slowly dripping the solution A for 1h, continuing to react for 5h, stopping the reaction, and heating the reaction kettleCooling to room temperature to obtain a polymer solution;
s3, dropwise adding the polymer solution into excessive n-hexane to generate precipitation, and carrying out suction filtration to obtain a powder polymer;
s4, dissolving the powdery polymer with tetrahydrofuran, dripping the solution into excessive n-hexane to generate precipitate, filtering the precipitate to obtain the powdery polymer, and drying the powder polymer in vacuum.
The reaction equation in this example is as follows:
the embodiment also discloses a photoresist prepared from the ArF photoresist film-forming polymer, which is specifically: an ArF photoresist was prepared by adding 5g of the ArF photoresist film-forming polymer described above with 0.175g of 2- (adamantane-1-carbonyl) oxy) -1, 1-difluoroethanesulfonic acid (4-methylphenyl) diphenylsulfonium salt and 0.02g of trioctylamine to 85g of propylene glycol methyl ether acetate.
The present example also discloses a photolithographic pattern obtained by coating the above-mentioned prepared photoresist, baking at 110deg.C for 60s, and then performing exposure treatment with an exposure energy of 20mJ/cm 2 Baking at 110deg.C for 60s after exposure, and developing with tetramethylammonium hydroxide developer for 60 s.
Example 2
The present example discloses an ArF photoresist film-forming polymer prepared from 8.1g of norbornene new monomer, 5.4g of maleic anhydride, 1.8g of tert-butyl 5-norbornene-2-carboxylate and 0.82g of azobisisobutyronitrile as raw materials, wherein the norbornene new monomer was prepared by using preparation 2.
The embodiment also discloses a preparation method of the ArF photoresist film-forming polymer, which comprises the following steps:
s1, accurately weighing 8.1g of norbornene new monomer, 5.4g of maleic anhydride, 1.8g of 5-norbornene-2-carboxylic acid tert-butyl ester (cas 154970-45-3) and 0.82g of azodiisobutyronitrile at 25 ℃, and dissolving with 28g of tetrahydrofuran to obtain a solution A;
s2, a stirrer, a condenser pipe and a thermometer are arrangedInto a 100ml four-necked flask of (2), 20g of tetrahydrofuran was charged into N 2 Under the protection action, stirring and heating to about 65 ℃, slowly dropwise adding the solution A, after 1 hour of dropwise adding, continuing to react for 5 hours, stopping the reaction, and cooling the temperature of the reaction kettle to room temperature to obtain a polymer solution;
s3, dropwise adding the polymer solution into excessive petroleum ether to generate precipitation, and carrying out suction filtration to obtain a powder polymer;
s4, dissolving the powdery polymer with tetrahydrofuran, dripping the solution into excessive n-hexane to generate precipitate, filtering the precipitate to obtain the powdery polymer, and drying the powder polymer in vacuum.
The reaction equation in this example is as follows:
the embodiment also discloses a photoresist prepared from the ArF photoresist film-forming polymer, which is specifically: arF photoresist was prepared by adding 5g of the above ArF photoresist film-forming polymer with 0.12g of triphenylsulfonium salt of perfluorobutyl sulfonate and 0.01g of trioctylamine to 80g of propylene glycol methyl ether acetate.
The present example also discloses a photolithographic pattern obtained by coating the above-mentioned prepared photoresist, baking at 110deg.C for 60s, and then performing exposure treatment with an exposure energy of 20mJ/cm 2 Baking at 110deg.C for 60s after exposure, and developing with tetramethylammonium hydroxide developer for 60 s.
Example 3
The present example discloses an ArF photoresist film-forming polymer prepared from 6.4g of norbornene new monomer, 4.9g of maleic anhydride, 3.6g of tert-butyl 5-norbornene-2-carboxylate and 0.82g of azobisisobutyronitrile, wherein the norbornene new monomer was prepared by using preparation 3.
The embodiment also discloses a preparation method of the ArF photoresist film-forming polymer, which comprises the following steps:
s1, accurately weighing 6.4g of norbornene new monomer, 4.9g of maleic anhydride, 3.6g of 5-norbornene-2-carboxylic acid tert-butyl ester (cas 154970-45-3) and 0.82g of azodiisobutyronitrile at 25 ℃, and dissolving with 28g of tetrahydrofuran to obtain a solution A;
s2, 20g of tetrahydrofuran was charged into a 100ml four-necked flask equipped with a stirrer, a condenser and a thermometer, followed by N 2 Under the protection action, stirring and heating to about 65 ℃, slowly dropwise adding the solution A, after 1 hour of dropwise adding, continuing to react for 5 hours, stopping the reaction, and cooling the temperature of the reaction kettle to room temperature to obtain a polymer solution;
s3, dropwise adding the polymer solution into excessive petroleum ether to generate precipitation, and carrying out suction filtration to obtain a powder polymer;
s4, dissolving the powdery polymer with tetrahydrofuran, dripping the solution into excessive isopropanol to generate precipitate, filtering the precipitate to obtain the powdery polymer, and drying the powdery polymer in vacuum.
The reaction equation in this example is as follows:
the embodiment also discloses a photoresist prepared from the ArF photoresist film-forming polymer, which is specifically: arF photoresist was prepared by adding 5g of the above ArF photoresist film-forming polymer with 0.12g of triphenylsulfonium salt of perfluorobutyl sulfonate and 0.01g of trioctylamine to 80g of propylene glycol methyl ether acetate.
The present example also discloses a photolithographic pattern obtained by coating the above-mentioned prepared photoresist, baking at 110deg.C for 60s, and then performing exposure treatment with an exposure energy of 20mJ/cm 2 Baking at 110deg.C for 60s after exposure, and developing with tetramethylammonium hydroxide developer for 60 s.
Comparative example
Comparative example 1
A photoetching pattern adopts the following preparation method:
p1, accurately weighing 4.9g of maleic anhydride, 9g of tert-butyl 5-norbornene-2-carboxylate (cas 154970-45-3) and 0.82g of azobisisobutyronitrile at 25 ℃, and dissolving with 28g of tetrahydrofuran to obtain a solution A;
p2, at 100 with stirrer, condenser and thermometerInto a ml four-necked flask, 20g of tetrahydrofuran was charged and the flask was charged with a solution of N 2 Under the protection action, stirring and heating to about 65 ℃, slowly dropwise adding the solution A, after 1 hour of dropwise adding, continuing to react for 5 hours, stopping the reaction, and cooling the temperature of the reaction kettle to room temperature to obtain a polymer solution;
p3, dropwise adding the polymer solution into excessive petroleum ether to generate precipitation, and carrying out suction filtration to obtain a powder polymer;
and P4, dissolving the powder polymer by using tetrahydrofuran, dropwise adding the polymer into excessive isopropanol to generate precipitate, filtering to obtain the powder polymer, and drying in vacuum to obtain the ArF photoresist film-forming polymer.
P5, adding 5g of ArF photoresist film-forming polymer and 0.12g of triphenylsulfonium perfluoro-butyl sulfonate and 0.01g of trioctylamine into 80g of propylene glycol methyl ether acetate to prepare ArF photoresist;
p6, after the prepared photoresist is coated, baking is carried out for 60s at 110 ℃, and then exposure treatment is carried out, wherein the exposure energy is 20mJ/cm 2 Baking at 110 ℃ for 60s after exposure, and finally developing for 60s by using tetramethylammonium hydroxide developer to obtain the photoetching pattern.
Detection method
The heat resistance, adhesion property and etch resistance of the photolithographic patterns prepared in examples 1 to 3 and comparative example 1 were tested using the following protocol:
1. adhesion performance test:
instrument: hitachi S-4800 scanning electron microscope;
the testing method comprises the following steps: and observing the photoresist pattern of the test sample to be reversed or fallen.
2. Etch resistance:
the testing method comprises the following steps: and etching the photoresist by adopting oxygen reaction ions, wherein the oxygen flow is 200sccm, and recording the film thickness and etching duration of the test sample before and after etching.
The relative etch rate sample etch rate/comparative etch was calculated.
The heat resistance, adhesion property and etching resistance of the test samples of examples 1 to 3 and comparative example 1 are shown in Table 1.
Table 1 examples 1-3 comparative example 1 table of data that can be tested
Referring to Table 1, in combination with examples 1 to 3 and comparative example 1, it can be seen that the photoresists prepared in examples 1 to 3 are free from pouring and falling off after development, and have significantly better adhesion than comparative example 1, indicating that the introduction of a norbornene new monomer into the ArF photoresist film-forming polymer helps to reduce the brittleness of the photoresist and improve the adhesion performance of the prepared photoresist. This is probably due to the stronger polarity of the nitrile groups on the side chains of the norbornene new monomers, which can give the ArF photoresist film-forming polymer better adhesion, thereby improving the brittleness and adhesion of the photoresist prepared from the ArF photoresist film-forming polymer.
The photoresist etch rates obtained in examples 1-3 are all less than comparative example 1, demonstrating that the introduction of norbornene monomers and maleic anhydride into the ArF photoresist film-forming polymer forms a maleic anhydride-norbornene polymer by free radical polymerization, and the introduction of a cyclic structure in the polymer backbone contributes to improved photoresist etch resistance.
The present embodiment is merely illustrative of the present application and is not intended to be limiting, and those skilled in the art, after having read the present specification, may make modifications to the present embodiment without creative contribution as required, but is protected by patent laws within the scope of the claims of the present application.

Claims (9)

  1. An arf photoresist film forming polymer characterized by: comprises the following components in proportion:
    5-20mol% of norbornene new monomer;
    45-55mol% of maleic anhydride monomer;
    20-40mol% of tert-butyl 5-norbornene-2-carboxylate;
    the new norbornene monomer has the following structural formula:
    wherein R1 is an alkyl chain, X is an alkyl group containing a nitrile group, and Y is a methylene group or an oxygen atom.
  2. 2. The ArF photoresist film forming polymer of claim 1, wherein: the norbornene new monomer is obtained by reacting a cyclodiene monomer (a) with an olefin monomer (b) DA (Diels-Alder), and the reaction process is as follows:
    wherein (a) the monomer is one of cyclopentadiene and furan;
    (b) The monomer is N-substituted maleimide monomer, and the structural general formula is as follows:
    wherein R is a substituent containing a nitrile group.
  3. 3. The ArF photoresist film forming polymer of claim 2, wherein: the structure of the monomer (b) is one of the following structures:
  4. 4. a process for the preparation of an ArF photoresist film-forming polymer as claimed in any one of claims 1 to 3, characterized in that: the method comprises the following steps:
    s1, dissolving a norbornene new monomer, a maleic anhydride monomer, 5-norbornene-2-carboxylic acid tert-butyl ester and an initiator in a first solvent to obtain a solution A; heating the solution A to 60-90 ℃ under the protection of N2, and reacting for 8-20h to obtain a polymer solution;
    s2, dropwise adding the polymer solution into a second solvent, and performing suction filtration to obtain a white precipitate;
    s3, dissolving the white precipitate in a first solvent to obtain a polymer solution;
    s4, repeating the steps S2 and S3 1-2 times, and drying after suction filtration to obtain purified white copolymer powder.
  5. 5. A photoresist made from the ArF photoresist film forming polymer of any one of claims 1-3, wherein: the composition comprises the following components:
    an ArF photoresist film forming polymer;
    a photoacid generator;
    an alkaline additive;
    a third solvent;
    the weight ratio of the photoacid generator to the ArF photoresist film-forming polymer is (0.5-10): 100;
    the weight ratio of the alkaline additive to the ArF photoresist film-forming polymer is (0.05-1): 100;
    the weight ratio of the third solvent to the ArF photoresist film-forming polymer is 100: (5-15).
  6. 6. The photoresist made from the ArF photoresist film forming polymer of claim 5, wherein: the photoacid generator is one or more of diazonium salt, sulfonium salt, iodonium salt, sulfonyl diazomethane, N-hydroxy imide sulfonate, imine sulfonate, nitrobenzyl benzene sulfonate and oxime sulfonate.
  7. 7. The photoresist made from the ArF photoresist film forming polymer of claim 5, wherein: the alkaline additive is one or more of tetra-n-butyl ammonium hydroxide, tetrabutylammonium acetate, tri-n-octylamine, 2, 6-diisopropylaniline and triethanolamine.
  8. 8. The photoresist made from the ArF photoresist film forming polymer of claim 5, wherein: the third solvent is one or more of propylene glycol methyl ether acetate, ethyl lactate, ethyl acetate, 2-heptanone, ethylene glycol monomethyl ether acetate, cyclohexanone, methyl pentanone alcohol and 3-ethoxypropionic acid.
  9. 9. A lithographic pattern, characterized by: the photoresist prepared from the ArF photoresist film-forming polymer according to any one of claims 5 to 8, which is obtained by a coating, soft baking, exposure, intermediate baking, and development process.
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Citations (4)

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Publication number Priority date Publication date Assignee Title
KR20000015410A (en) * 1998-08-28 2000-03-15 김영환 New photoresist polymer and a composition using the new photoresist polymer
KR20010011767A (en) * 1999-07-30 2001-02-15 김영환 Novel photoresist polymer and photoresist composition containing it
CN1834785A (en) * 2006-04-19 2006-09-20 苏州华飞微电子材料有限公司 Silicon contg. 193nm negative photo resist and membrane forming resin
CN115536776A (en) * 2022-10-15 2022-12-30 瑞红(苏州)电子化学品股份有限公司 Resin for photoresist, preparation method thereof and photoresist prepared from resin

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20000015410A (en) * 1998-08-28 2000-03-15 김영환 New photoresist polymer and a composition using the new photoresist polymer
KR20010011767A (en) * 1999-07-30 2001-02-15 김영환 Novel photoresist polymer and photoresist composition containing it
CN1834785A (en) * 2006-04-19 2006-09-20 苏州华飞微电子材料有限公司 Silicon contg. 193nm negative photo resist and membrane forming resin
CN115536776A (en) * 2022-10-15 2022-12-30 瑞红(苏州)电子化学品股份有限公司 Resin for photoresist, preparation method thereof and photoresist prepared from resin

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