CN115160495B - Photoresist film-forming resin containing maleimide structure and preparation method thereof - Google Patents

Photoresist film-forming resin containing maleimide structure and preparation method thereof Download PDF

Info

Publication number
CN115160495B
CN115160495B CN202210975459.8A CN202210975459A CN115160495B CN 115160495 B CN115160495 B CN 115160495B CN 202210975459 A CN202210975459 A CN 202210975459A CN 115160495 B CN115160495 B CN 115160495B
Authority
CN
China
Prior art keywords
forming resin
maleimide
film
monomer
photoresist
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202210975459.8A
Other languages
Chinese (zh)
Other versions
CN115160495A (en
Inventor
盖景刚
韦南君
刘洋
李一博
孙义兴
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sichuan Huazao Hongcai Technology Co ltd
Original Assignee
Sichuan Huazao Hongcai Technology Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sichuan Huazao Hongcai Technology Co ltd filed Critical Sichuan Huazao Hongcai Technology Co ltd
Priority to CN202210975459.8A priority Critical patent/CN115160495B/en
Publication of CN115160495A publication Critical patent/CN115160495A/en
Application granted granted Critical
Publication of CN115160495B publication Critical patent/CN115160495B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • 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
    • C08F222/36—Amides or imides
    • C08F222/40—Imides, e.g. cyclic imides
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The invention belongs to the technical field of photoresist, and particularly relates to a photoresist film-forming resin containing a maleimide structure and a preparation method thereof. 193nm photoresist based on polymethyl methacrylate has the problems of low sensitivity, poor dry etching resistance, low substrate adhesion and the like. The invention provides a photoresist film-forming resin containing a maleimide structure, which has the following structural formula: (M 1-co-M2-co-M3); wherein M 1 is a para-acid and/or photo-sensitive unit, M 2 is a maleimide or N-substituted maleimide unit, M 3 is selected from polar group-containing monomers, and the unit number ratio of M 1:M2:M3 is M 1:m2:m3 = (3-5): (2-6): (1-3). The photoresist has good sensitivity, thermal stability, adhesiveness and developability, and has good application on 193nm photoresist and main film forming resin of electron beam photoresist.

Description

Photoresist film-forming resin containing maleimide structure and preparation method thereof
Technical Field
The invention belongs to the technical field of photoresist, and particularly relates to a photoresist film-forming resin containing a maleimide structure and a preparation method thereof.
Background
In the development process of ultraviolet lithography technology, the G line (436 nm) and I line (365 nm) lithography generated by a high-pressure mercury lamp is utilized at first, the application is wide and the use is long, and a phenolic resin/diazonaphthoquinone system is commonly used as a photoresist. Due to the pursuit of high performance and high resolution, photolithography technology is advancing toward shorter wavelengths. Deep Ultraviolet (DUV) lithography using KrF excimer laser (248 nm), arF excimer laser (193 nm), and F 2 excimer laser (157 nm) as light sources mainly uses polystyrene derivatives, polymethacrylate derivatives, and fluoropolymers as photoresists, respectively. Among them, the F 2 excimer laser is abandoned for economic reasons and the like. In recent years, techniques such as EUV extreme ultraviolet (13.5 nm) lithography, electron beam lithography, plasma lithography and the like have been developed, and photoresists commonly used for the techniques include molecular glass systems, organic-inorganic hybrid materials and the like.
ArF excimer laser (193 nm) lithography is widely used because of its technical and economic integration over other lithography techniques. In the beginning of 193nm lithography, 248nm lithography of polystyrene derivative photoresists has been continuously used, but the benzene ring on the polymer molecular chain has a large amount of ultraviolet absorption around 193nm, so that new photoresist systems are required to be developed. The main film-forming resins of 193nm photoresists are currently mainly poly (meth) acrylate systems, maleic anhydride copolymer systems, norbornene polymer systems, cyclized polymer systems, and the like.
Acrylate polymers are commonly used as 193nm photoresists, and the polymer molecular chains thereof have no conjugated structure such as double bonds and benzene rings, so that the polymer has high transparency near 193 nm. The side chain ester part of the acrylic ester polymer is subjected to high-energy photon bombardment to generate a free radical through Norrish I type fracture, the free radical is further transferred to cause the main chain to be broken, and the formed small molecule fragments can be dissolved in the developer. However, most of the molecular chains of the acrylic polymers have a simple linear structure and high oxygen content, so that the acrylic esters have poor plasma etching resistance, and the simple hydrocarbon structure of the molecular chains of the polymers has low photosensitivity and poor adhesion with the substrate.
Disclosure of Invention
193Nm photoresist based on polymethyl methacrylate has excellent image properties, but also has problems such as low sensitivity, poor dry etching resistance, low substrate adhesion, and the like. The invention provides a photoresist film-forming resin containing a maleimide structure and a preparation method of the film-forming resin. The photoresist film-forming resin containing the maleimide structure has good light sensitivity or acid sensitivity, excellent thermal stability and plasma etching resistance, good adhesion with a substrate and good developability. Suitable for use as a host film forming resin for 193nm photoresist or electron beam photoresist.
In order to achieve the above purpose, the present invention provides the following technical solutions:
first, the present invention provides an acrylic film-forming resin containing a maleimide structure, having the structural formula:
(M1-co-M2-co-M3)；
Wherein M 1 is a para-acid and/or photo-sensitive unit, M 2 is a maleimide or N-substituted maleimide unit, M 3 is selected from polar group-containing monomers, and the unit number ratio of M 1:M2:M3 is M 1:m2:m3 = (3-5): (2-6): (1-3).
Further, the M 1 is selected from acid or photosensitive acrylate monomers or photosensitive alpha-methyl styrene, and has the following structural general formula:
wherein, in the chemical general formula of M 1 -0, R 1 is independently selected from H, cl or CH 3;R2 and is independently selected from methyl, adamantyl, 2-methyladamantanyl, 2-ethyladamantanyl or hexafluorobutyl.
Still further, the M 1 -0 is selected from at least one of methyl α -chloroacrylate, adamantyl 1-acrylate, 2-methacryloxy-2-methyladamantane, 2-methyladamantan-2-yl acrylate, 1-ethyl-2-methacryloxy adamantane, or hexafluorobutyl methacrylate.
Preferably, said M 1 is selected from the following compounds:
Further, the M 2 is selected from maleimide or N-substituted maleimide units, and has the following structural general formula:
Wherein R 3 is independently selected from H, CH 3 or phenyl.
Still further, the M 2 is selected from maleimide, N-methylmaleimide, or N-phenylmaleimide.
Preferably, said M 2 is selected from the following compounds:
Further, the M 3 is selected from hydroxyl-containing polar group monomers, and has a structural general formula as follows:
Wherein R 4 is independently selected from H or CH 3,R5 is selected from hydroxyadamantanyl or hydroxypropyl.
Still further, the M 3 is selected from 3-hydroxy-1-methacryloxy adamantane, 1-acryloxy-3-hydroxyadamantane, or 3-hydroxypropyl methacrylate.
Preferably, said M 3 is selected from the following compounds:
preferably, the structural formula of the maleimide structure-containing acrylic ester film-forming resin is as follows:
Wherein R 1 is independently selected from H, cl or CH 3;R2 is independently selected from methyl, adamantyl, 2-methyladamantanyl, 2-ethyladamantanyl, or hexafluorobutyl; r 3 is independently selected from H, CH 3 or phenyl; r 4 is independently selected from H or CH 3;R5 is independently selected from hydroxyadamantanyl or hydroxypropyl; m 1＝3～5000,m2＝2～6000,m3 =1 to 3000, and m 1:m2:m3 = (3 to 5): (2 to 6): (1 to 3).
Most preferably, the maleimide structure-containing acrylate film-forming resin of the present invention is selected from any of the following structures:
Wherein the maleimide structure-containing acrylate film-forming resin has a number average molecular weight of 500 to 100000, a weight average molecular weight of 500 to 500000, and/or a molecular weight distribution index of 1.0 to 5.0.
Secondly, the invention provides a preparation method of the acrylic ester film-forming resin containing the maleimide structure, which comprises the following steps:
a. Uniformly mixing M 1 monomer, M 2 monomer and M 3 monomer corresponding to functional units on a film-forming resin molecular chain with an initiator and an organic solvent according to a proportion; the M 1、M2、M3 monomer is selected from any one of the compounds defined above;
b. c, carrying out polymerization reaction on the mixed system obtained in the step a under the protection of inert atmosphere;
c. after the reaction is finished, the obtained mixed system is added into a precipitator, and the precipitate is separated and dried, thus obtaining the catalyst.
In the step a, the monomer M 1 used in the polymerization reaction is selected from protonic acid, a photosensitive acrylate monomer or an alpha-methylstyrene monomer, the monomer M 2 is selected from maleimide or N-substituted maleimide monomer, the monomer M 3 is selected from hydroxyl-containing polar group monomer, and the unit number ratio of M 1:M2:M3 is M 1:m2:m3 = (3-5): 2-6): 1-3.
In the step a, the initiator is at least one of azodiisobutyronitrile, azodiisoheptonitrile, dibenzoyl peroxide, cyclohexanone peroxide, dicumyl peroxide, di-tert-butyl peroxide, cumene hydroperoxide or tert-butyl hydroperoxide.
Wherein, in the step a, the amount of the initiator is 0.1 to 10 percent of the total amount of three monomers used in the polymerization reaction.
Wherein in step a, the organic solvent is selected from at least one of tetrahydrofuran, dioxane, acetone, acetonitrile, cyclohexanone, benzene, toluene, chlorobenzene, xylene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane, trichloroethane, ethyl acetate, butyl acetate, DMF, DMAc, NMP and DMSO.
In the step a, the dosage of the organic solvent is 10-100 mL/g of the total dosage of the mixed reaction system.
In the step b, the inert atmosphere is nitrogen or argon in the polymerization reaction.
In the step b, the initiation temperature of the polymerization reaction is 50-90 ℃, and the duration reaction time is 6-48 h.
In the step c, the precipitant is at least one of isopentane, n-pentane, trimethylpentane, isooctane, deionized water, methanol, ethanol, n-hexane, cyclohexane, diethyl ether or petroleum ether. Preferably, the precipitant is petroleum ether, n-hexane, cyclohexane.
In the step c, the volume of the precipitant is 10-100 times of the volume of the organic solvent for polymerization reaction.
Finally, the invention also provides application of the acrylic ester film-forming resin containing the maleimide structure in the field of photoresist.
The beneficial effects are that: the invention prepares a series of acrylic ester-maleimide copolymer which is prepared by using light-sensitive or acid-sensitive alpha-methyl styrene or acrylic ester unit and N-substituted maleimide unit in a way of copolymerization of hydroxyl-containing polar group acrylic ester unit and is used as a main film forming resin of a photoresist. The alpha-methyl styrene, alpha-methyl chloroacrylate or hexafluorobutyl methacrylate can obviously enhance the sensitivity of the polymer to ultraviolet light, so that the molecular chain breakage of the polymer is increased after the polymer is irradiated by ultraviolet light. The adamantyl acrylate series is an acid sensitive unit, hydrophobic-hydrophilic conversion can be realized by photo-generated proton acid to catalyze the side group to drop, so that the polymer after exposure is dissolved in a developing solution, and the polymer becomes a chemically amplified photoresist. The N-substituted maleimide is connected into the molecular main chain of the polymer, so that the thermal stability and the glass transition temperature of the polymer resin can be obviously improved. Hydroxyl groups are polar groups, and the incorporation of the polar groups into the molecular chain can modulate the hydrophilic-lipophilic balance, substrate adhesion, and developability of the polymer.
Therefore, the copolymer containing the maleimide structure provided by the invention has good sensitivity, thermal stability, adhesiveness, developability and the like, and can be well applied to main film forming resin directions of 193nm photoresist and electron beam photoresist because the molecular chain of the copolymer does not contain structures such as benzene rings, conjugated double bonds and the like. Compared with the existing photoresist film-forming resin, the film-forming resin disclosed by the invention has relatively uniform molecular weight distribution, and low molecular weight dispersibility is beneficial to improving the photosensitivity and thermal stability of the resin.
Drawings
FIG. 1 is a Fourier transform infrared transmission spectrum of P (AA-MI-HAA) -352 of example 1 of the present invention;
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of P (AA-MI-HAA) -352 of example 1 of the present invention;
FIG. 3 is an ultraviolet absorption spectrum of P (AA-MI-HAA) -352 of example 1 of the present invention;
FIG. 4 is a molecular weight and molecular weight distribution diagram of P (AA-MI-HAA) -352 of example 1 of the present invention;
FIG. 5 is a thermal weight loss curve of P (AA-MI-HAA) -352 of example 1 of the invention;
FIG. 6 is a DSC curve of P (AA-MI-HAA) -352 of example 1 of the present invention.
Detailed Description
Modification of acrylates often involves improvements in polymer sensitivity, etch resistance, adhesion, and the like. The corresponding method is to access relevant functional group units to the polymer molecular chain in a copolymerization mode, so that the corresponding performance of the polymer is improved. In general, the etching resistance and the thermal stability of the polymer resin can be obviously improved by connecting a multi-alicyclic structure to a main chain or a side chain of the polymer, and commonly used structures are adamantane, norbornene derivatives, tetracyclododecene derivatives and the like. The units of alpha-methyl styrene, alpha-methyl chloroacrylate, hexafluorobutyl methacrylate and the like can obviously improve the light sensitivity of the polymer resin. Polar groups such as hydroxyl groups and carboxyl groups can improve the hydrophilicity and substrate adhesiveness of the polymer.
The invention aims to provide a photoresist film-forming resin containing a maleimide structure and a preparation method of the film-forming resin. The photoresist film-forming resin containing the maleimide structure has good light sensitivity or acid sensitivity, excellent thermal stability and plasma etching resistance, good adhesion with a substrate and good developability. Suitable for use as a host film forming resin for 193nm photoresist or electron beam photoresist.
The invention firstly discloses the following technical scheme:
the structural formula of the maleimide structure-containing acrylic ester film-forming resin is as follows:
(M1-co-M2-co-M3)；
Wherein M 1 is an acid and/or light-sensitive unit, M 2 is a maleimide or N-substituted maleimide unit, M 3 is a polar group-containing monomer, and the unit number ratio of M 1:M2:M3 is M 1:m2:m3 = (3-5): (2-6): (1-3). The invention controls the proportion of the acid and/or the photosensitive unit M 1 to 30-50%, which can ensure enough acid or photosensitive sensitivity; the proportion of the maleimide or N-substituted maleimide unit M 2 is 20-60 percent, so as to regulate and control the cyclic structure of the molecular main chain; the proportion of the hydroxyl-containing structural unit M 3 is 10-30%, and is used for controlling the clear water-lipophilic balance and the adhesion capability of the substrate. When the amount of a certain monomer is reduced to cause the corresponding performance to be insufficient, the excessive amount can cause the insufficient amount of the rest monomer to cause the corresponding performance to be reduced. The maleimide is enophile, can be well copolymerized with acrylic ester alternately, and meanwhile, intramolecular and intermolecular hydrogen bonds are formed between imine groups and hydroxyl groups, so that the mechanical strength and heat resistance of the polymer can be improved. If other monomers are used for replacement, the corresponding effect is difficult to obtain.
In the scheme, the molecular chain side chain of the film-forming resin contains acid or photosensitive groups, and the sensitivity of the film-forming resin can be improved by acid catalysis of molecular side chain fracture or photoinduced molecular side chain fracture. The maleimide structure on the film-forming resin main chain can increase the molecular chain ring-shaped structure, improve the rigidity and the thermal stability of the molecular chain and improve the etching resistance of the film-forming resin. The hydrophilic-lipophilic balance of the polymer can be controlled by connecting the polar units on the molecular chain of the film-forming resin, so that the substrate adhesiveness and the developability of the film-forming resin are improved.
According to some preferred embodiments of the invention, the film-forming resin has the formula,
M 1 is an acid and/or light-sensitive acrylic ester monomer or light-sensitive alpha-methyl styrene, wherein the acid is usually proton acid generated by photo acid generators such as sulfonium salt, iodonium salt and the like under ultraviolet irradiation, and the structural general formula of the acrylic ester monomer or light-sensitive alpha-methyl styrene is as follows:
Wherein R 1 is H, cl or CH 3.R2 is methyl, adamantyl, 2-methyladamantanyl, 2-ethyladamantanyl or hexafluorobutyl. The corresponding monomers are alpha-methyl chloroacrylate, 1-adamantyl acrylate, 2-methacryloxy-2-methyladamantane, 2-methyladamantan-2-yl acrylate, 1-ethyl-2-methacryloxy adamantane and hexafluorobutyl methacrylate, and the corresponding structural formulas are as follows:
M 2 is a maleimide or N-substituted maleimide unit of the general structural formula:
Wherein R 3 is H, CH 3 or phenyl. The corresponding monomers are maleimide, N-methylmaleimide and N-phenylmaleimide, and the corresponding structural formulas are as follows:
M 3 is a monomer containing hydroxyl polar groups, and the structural general formula is as follows:
wherein R 4 is H or CH 3.R5 is hydroxyadamantanyl or hydroxypropyl. The corresponding monomers are 3-hydroxy-1-methacryloxy adamantane, 1-acryloxy-3-hydroxyadamantane and 3-hydroxypropyl methacrylate, and the corresponding structural formulas are as follows:
according to some preferred embodiments of the invention, the film-forming resin has the following structural formula:
Wherein R 1 is H, cl or CH 3.R2 is methyl, adamantyl, 2-methyladamantanyl, 2-ethyladamantanyl or hexafluorobutyl. R 3 is H, CH 3 or phenyl. R 4 is H or CH 3.R5 is hydroxyadamantanyl or hydroxypropyl .m1＝3～5000,m2＝2～6000,m3＝1～3000.m1:m2:m3＝(3～5):(2～6):(1～3).
According to some preferred embodiments of the present invention, the film-forming resin has, but is not limited to, any one of the following structural formulas:
According to some preferred embodiments of the present invention, the film-forming resin has a number average molecular weight of 500 to 100000, a weight average molecular weight of 500 to 500000, and/or a molecular weight distribution index of 1.0 to 5.0.
The invention provides a preparation method of the film-forming resin, which comprises the following preparation steps:
a. Preparing a mixed reaction system from M 1 monomer, M 2 monomer, M 3 monomer, a small amount of initiator and a proper amount of organic solvent corresponding to functional units on a molecular chain of the film-forming resin;
b. Under the protection of inert atmosphere, initiating the polymerization reaction of the mixed reaction system under the condition of proper temperature, and keeping the temperature for a period of time;
c. And after the reaction is finished, dropwise adding the obtained mixed system into a precipitator, separating precipitate, and drying under certain conditions to obtain the film-forming resin.
According to some preferred embodiments of the invention, the inert atmosphere used in the polymerization reaction is one of nitrogen or argon.
According to some preferred embodiments of the present invention, the monomer M 1 used in the polymerization is an acid or light sensitive acrylate monomer or an alpha-methylstyrene monomer, the monomer M 2 is an N-substituted maleimide monomer, the monomer M 3 is a hydroxyl group-containing polar group monomer, and the unit number ratio of M 1:M2:M3 is M 1:m2:m3 = (3-5): 2-6): 1-3.
According to some preferred embodiments of the present invention, the initiator requires a low decomposition temperature, high initiation efficiency, and is soluble in organic solvents. Typical initiators are azobisisobutyronitrile, azobisisoheptonitrile, dibenzoyl peroxide, cyclohexanone peroxide, dicumyl peroxide, di-t-butyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, etc., and the typical compound initiators can achieve better initiation effect.
According to some preferred embodiments of the invention, the initiator is used in an amount of 0.1 to 10% of the total mass of the three monomers used in the polymerization reaction.
According to some preferred embodiments of the present invention, the organic solvent is required to be capable of dissolving the reaction monomer, capable of dissolving the reaction polymer, and having a boiling point higher than the decomposition temperature of the initiator. The organic solvent is one or more of tetrahydrofuran, dioxane, acetone, acetonitrile, cyclohexanone, benzene, toluene, chlorobenzene, xylene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane, trichloroethane, ethyl acetate, butyl acetate, DMF, DMAc, NMP and DMSO.
According to some preferred embodiments of the present invention, the amount of the organic solvent required for the polymerization reaction is (10 to 100) mL/g of the total amount of the mixed reaction system.
According to some preferred embodiments of the present invention, the polymerization reaction of the mixed reaction system is initiated at a temperature of typically 50 to 90 ℃ for a reaction time of typically 6 to 48 hours.
According to some preferred embodiments of the present invention, the precipitant is required to be miscible with the reaction solvent, but not to dissolve or only slightly dissolve the resulting polymer. The precipitant is one or more of isopentane, n-pentane, trimethylpentane, isooctane, deionized water, methanol, ethanol, n-hexane, cyclohexane, diethyl ether and petroleum ether, wherein the low-polarity solvents such as petroleum ether, n-hexane and cyclohexane have better precipitant effect.
According to some preferred embodiments of the invention, the volume of the precipitant is 10 to 100 times the volume of the organic solvent used for the polymerization reaction.
According to the technical scheme of the invention, a specific preparation method of the photoresist film-forming resin containing the maleimide structure comprises the following steps:
the reaction device is flushed by nitrogen for 10 to 30 minutes, and the reaction device is sealed. And dissolving a certain proportion of M 1 monomer, M 2 monomer, M 3 monomer and an initiator in a proper amount of solvent to obtain a mixed reaction system. The mixed reaction system is added into the reaction device drop by drop, and heated and reacted for a period of time at a proper temperature. And finally, dripping the mixed solution obtained by the reaction into a precipitator, filtering and drying to obtain the film-forming resin.
Wherein, the initiator can be selected from one or more of azodiisobutyronitrile, azodiisoheptonitrile, dibenzoyl peroxide, cyclohexanone peroxide, dicumyl peroxide, di-tert-butyl peroxide, cumene hydroperoxide, tert-butyl hydroperoxide and the like, and the dosage of the initiator is preferably 0.1-10 percent of the total amount of three monomers used in the polymerization reaction.
The organic solvent can be selected from one or more of tetrahydrofuran, dioxane, acetone, acetonitrile, cyclohexanone, benzene, toluene, chlorobenzene, xylene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane, trichloroethane, ethyl acetate, butyl acetate, DMF, DMAc, NMP and DMSO. Preferably, the required amount of the organic solvent is (10-100) mL/g of the total amount of the mixed reaction system.
According to some preferred embodiments of the invention, the precipitant is selected from one or more of isopentane, n-pentane, trimethylpentane, isooctane, deionized water, methanol, ethanol, n-hexane, cyclohexane, diethyl ether, and petroleum ether. Preferably, the volume of the precipitant is 10 to 100 times the volume of the organic solvent for polymerization.
The scheme of the present invention will be explained below with reference to examples. It will be appreciated by those skilled in the art that the following examples are illustrative of the present invention and should not be construed as limiting the scope of the invention. The examples are not to be construed as limiting the specific techniques or conditions described in the literature in this field or as per the specifications of the product. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
The method comprises the following steps of preparing a photoresist film-forming resin containing a maleimide structure:
The reaction apparatus of the combination of round bottom flask and bulb condenser was sealed after 30 minutes of nitrogen flushing, injected with a small amount of tetrahydrofuran, and placed in an 80 ℃ oil bath environment for preheating. 2-methyladamantan-2-yl acrylate, maleimide, 1-acryloxy-3-hydroxyadamantane, and azobisisobutyronitrile were dissolved in tetrahydrofuran at a ratio of 6:10:4:1 to give a mixed reaction system of about 0.1 g/mL. The mixed reaction system is added into the reaction device drop by drop, and the reaction is finished after 24 hours. And (3) dripping the mixed solution obtained by the reaction into petroleum ether, and filtering to obtain polymer solid. The solid was dissolved in tetrahydrofuran, precipitated again, and purified three times repeatedly. The obtained solid is naturally air-dried for 24 hours in a fume hood, and then is dried for 48 hours at 80 ℃ in a vacuum drying oven, and the dried solid is put into a brown reagent bottle and stored in a dark place, so that the conversion rate of the photoresist film-forming resin is about 78%. The polymer was designated P (AA-MI-HAA) -352.
According to the infrared spectrum and the nuclear magnetic resonance hydrogen spectrum, the structural formula of the obtained photoresist resin is as follows:
Infrared transmission spectra were obtained by fourier transform infrared spectrometer Nicolet is50 (thermo fisher, usa) under infrared light in the range 4000-400 cm -1. According to the infrared transmission spectrum (figure 1), the absorption peak at 3480cm -1 is the O-H telescopic vibration absorption band of hydroxyl, and the hydroxyl structure on the molecular chain of the polymer is proved. 3260cm -1 is the N-H telescopic vibration absorption band of amine groups, proving the imine structure on the molecular chain of the polymer. The absorption peak at 1730cm -1 is carbonyl stretching vibration absorption band, which proves the ester group structure on the polymer molecular chain.
1-H Nuclear magnetic resonance was obtained by AVANCE III spectrometer (Brookfield, germany) under 400MHz frequency Tetramethylsilane (TMS) as internal chemical shift standard and CDCl 3 as solvent. According to nuclear magnetic resonance hydrogen spectrum (fig. 2), 2.0751ppm is the chemical shift of the closest methylene hydrogen to the ester group on the adamantyl group, 3.6780ppm is the chemical shift of the hydrogen on the methine group attached to the imide group, 4.6898ppm is the chemical shift of the hydroxy hydrogen on the hydroxyadamantanyl group.
The ultraviolet absorption spectrum is obtained by using tetrahydrofuran as a solvent in a range of 185-400 nm by an ultraviolet-visible-infrared spectrophotometer UV-3600 (Shimadzu). According to the ultraviolet absorption spectrum (FIG. 3), the polymer has only a small amount of ultraviolet absorption in the range of 185-300nm, and the polymer has better transparency in the ultraviolet region.
Molecular weight and molecular weight distribution were obtained by gel permeation chromatograph HLC-8320GPC (Tosoh Corp., japan) with polystyrene as a standard in THF at 25℃and flow rate of 1.0mL min -1. According to the molecular weight and molecular weight distribution (FIG. 4), the weight average molecular weight of the polymer was 1233, the number average molecular weight was 726, the molecular weight distribution index was 1.70, and the molecular weight distribution was uniform.
The thermogravimetric curve was obtained by heating each sample (5-8 mg) from 35℃to 500℃by TGA2 thermogravimetric analyzer (Metrehler, switzerland) at 10℃for -1 in a nitrogen atmosphere at a flow rate of 10mL for -1. According to the thermal weight loss curve (fig. 5), the polymer starts to decompose rapidly at around 240 ℃, which indicates that the polymer has better heat resistance and does not decompose thermally during soft and hard baking.
DSC curves were obtained by heating each sample (5-8 mg) from 20 ℃ to 200 ℃ in a dry nitrogen atmosphere by differential scanning calorimeter DSC1 (german relaxation resistance) at a heating rate of 10 ℃ min -1. According to the DSC curve (FIG. 6), the glass transition temperature of the polymer is about 127℃and the glass transition temperature of the polymer is higher than the usual soft and hard bake temperatures of the photoresist, 90-120℃and the polymer resin is not thermally deformed during baking.
Example 2
The reaction apparatus of the combination of round bottom flask and bulb condenser was sealed after 30 minutes of nitrogen flushing, injected with a small amount of tetrahydrofuran, and placed in an 80 ℃ oil bath environment for preheating. 2-methacryloxy-2-methyladamantane, N-methylmaleimide, 3-hydroxy-1-methacryloxy-adamantane and azobisisobutyronitrile were dissolved in tetrahydrofuran in a ratio of 8:8:4:1 to give a mixed reaction system of about 0.1 g/mL. The mixed reaction system is added into the reaction device drop by drop, and the reaction is finished after 24 hours. And (3) dripping the mixed solution obtained by the reaction into n-hexane, and filtering to obtain polymer solid. The solid was dissolved in tetrahydrofuran, precipitated again, and purified three times repeatedly. The obtained solid is naturally air-dried for 24 hours in a fume hood, and then is dried for 48 hours at 80 ℃ in a vacuum drying oven, and the dried solid is put into a brown reagent bottle and stored in a dark place, so that the conversion rate of the photoresist film-forming resin is about 82%.
Example 3
The reaction apparatus of the combination of round bottom flask and bulb condenser was sealed after 30 minutes of nitrogen flushing, injected with a small amount of tetrahydrofuran, and placed in an 80 ℃ oil bath environment for preheating. 1-ethyl-2-methacryloxy adamantane, N-phenyl maleimide, 3-hydroxypropyl methacrylate and azobisisobutyronitrile were dissolved in tetrahydrofuran in a ratio of 10:6:4:1 to give a mixed reaction system of about 0.1 g/mL. The mixed reaction system is added into the reaction device drop by drop, and the reaction is finished after 24 hours. The mixed solution obtained by the reaction is dripped into cyclohexane, and polymer solid is obtained after filtration. The solid was dissolved in tetrahydrofuran, precipitated again, and purified three times repeatedly. The obtained solid is naturally air-dried for 24 hours in a fume hood, and then is dried for 48 hours at 80 ℃ in a vacuum drying oven, and the dried solid is put into a brown reagent bottle and stored in a dark place, so that the conversion rate of the photoresist film-forming resin is about 74%.
It is to be noted that the particular features, structures, materials, or characteristics described in this specification may be combined in any suitable manner in any one or more embodiments. Furthermore, the various embodiments described in this specification, as well as the features of the various embodiments, can be combined and combined by one skilled in the art without contradiction.

Claims (6)

1. An acrylic ester film-forming resin containing a maleimide structure, characterized in that: selected from the following structures:
m 1＝3～5000,m2＝2～6000,m3 =1 to 3000, and m 1:m2:m3 = (3 to 5): (2 to 6): (1 to 3).
2. The maleimide structured acrylate film-forming resin according to claim 1, wherein: the maleimide structure-containing acrylate film-forming resin has a number average molecular weight of 726, a weight average molecular weight of 1233, and/or a molecular weight distribution index of 1.7.
3. The method for producing an acrylic acid ester film-forming resin containing a maleimide structure according to claim 1 or 2, characterized in that: the method comprises the following steps:
a. Uniformly mixing 2-methyladamantan-2-yl acrylate monomer, maleimide monomer and 1-acryloyloxy-3-hydroxyadamantan monomer corresponding to functional units on a film-forming resin molecular chain with an initiator and an organic solvent according to a proportion;
b. c, carrying out polymerization reaction on the mixed system obtained in the step a under the protection of inert atmosphere;
c. after the reaction is finished, the obtained mixed system is added into a precipitator, and the precipitate is separated and dried, thus obtaining the catalyst.
4. The method for producing a maleimide structure-containing acrylic acid ester film-forming resin according to claim 3, wherein: at least one of the following is satisfied:
in the step a, the ratio of the number of the acrylic acid 2-methyladamantan-2-yl ester monomer, the maleimide monomer and the 1-acryloyloxy-3-hydroxyadamantan monomer units used in the polymerization reaction is m 1:m2:m3 = (3-5): 2-6): 1-3;
In the step a, the initiator is at least one of azodiisobutyronitrile, azodiisoheptonitrile, dibenzoyl peroxide, cyclohexanone peroxide, dicumyl peroxide, di-tert-butyl peroxide, cumene hydroperoxide or tert-butyl hydroperoxide;
In the step a, the amount of the initiator is 0.1-10% of the total mass of three monomers used in the polymerization reaction;
In the step a, the organic solvent is selected from at least one of tetrahydrofuran, dioxane, acetone, acetonitrile, cyclohexanone, benzene, toluene, chlorobenzene, xylene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane, trichloroethane, ethyl acetate, butyl acetate, DMF, DMAc, NMP and DMSO;
in the step a, the dosage of the organic solvent is 10-100 mL/g of the total dosage of the mixed reaction system;
in the step b, in the polymerization reaction, the inert atmosphere is nitrogen or argon;
in the step b, the initiation temperature of the polymerization reaction is 50-90 ℃, and the duration reaction time is 6-48 h;
in the step c, the precipitant is at least one of isopentane, n-pentane, trimethylpentane, isooctane, deionized water, methanol, ethanol, n-hexane, cyclohexane, diethyl ether or petroleum ether;
In the step c, the volume of the precipitant is 10-100 times of the volume of the organic solvent for polymerization reaction.
5. The method for producing a maleimide structure-containing acrylic acid ester film-forming resin according to claim 4, wherein: in the step c, the precipitant is petroleum ether, n-hexane or cyclohexane.
6. Use of the maleimide structure-containing acrylate film-forming resin according to claim 1 or 2 in the field of photoresists.
CN202210975459.8A 2022-08-15 2022-08-15 Photoresist film-forming resin containing maleimide structure and preparation method thereof Active CN115160495B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210975459.8A CN115160495B (en) 2022-08-15 2022-08-15 Photoresist film-forming resin containing maleimide structure and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210975459.8A CN115160495B (en) 2022-08-15 2022-08-15 Photoresist film-forming resin containing maleimide structure and preparation method thereof

Publications (2)

Publication Number Publication Date
CN115160495A CN115160495A (en) 2022-10-11
CN115160495B true CN115160495B (en) 2024-05-14

Family

ID=83479010

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210975459.8A Active CN115160495B (en) 2022-08-15 2022-08-15 Photoresist film-forming resin containing maleimide structure and preparation method thereof

Country Status (1)

Country Link
CN (1) CN115160495B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115536776B (en) * 2022-10-15 2023-08-29 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

Citations (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63154712A (en) * 1986-12-17 1988-06-28 Japan Synthetic Rubber Co Ltd Production of transparent heat-resistant resin
JP2000204126A (en) * 1999-01-14 2000-07-25 Nippon Shokubai Co Ltd New maleimide-based copolymer
JP2002323771A (en) * 2001-02-22 2002-11-08 Nissan Chem Ind Ltd Composition for forming antireflection film for lithography
KR20050029420A (en) * 2003-09-22 2005-03-28 한국과학기술연구원 A thermally crosslinkable polymer for a bottom anti-reflective coating for photolithography, a composition for preparing a bottom anti-reflective coating using the same, and preparation method thereof
CN103229101A (en) * 2010-11-30 2013-07-31 日产化学工业株式会社 Photosensitive resin composition for microlenses
CN104040432A (en) * 2012-01-19 2014-09-10 日产化学工业株式会社 Negative photosensitive resin composition
CN104641294A (en) * 2012-10-02 2015-05-20 日产化学工业株式会社 Negative photosensitive resin composition
CN104650281A (en) * 2014-12-26 2015-05-27 北京鼎材科技有限公司 Alkali-soluble resin polymer for color light filter and light-sensitive resin composition
CN106324985A (en) * 2015-06-30 2017-01-11 东友精细化工有限公司 Colored photosensitive resin composition, color filter and liquid crystal display device
CN107003607A (en) * 2014-12-04 2017-08-01 日产化学工业株式会社 Positive type photosensitive organic compound
CN111234094A (en) * 2018-11-28 2020-06-05 北京鼎材科技有限公司 Modified dye, photosensitive resin composition containing same and application
CN111886545A (en) * 2018-03-29 2020-11-03 太阳油墨制造株式会社 Photocurable/thermosetting resin composition, dry film, cured product, and printed wiring board
CN111944090A (en) * 2019-06-06 2020-11-17 上海函泰电子科技有限公司 Polymer resin and preparation method and application thereof
CN112534352A (en) * 2018-08-21 2021-03-19 Jsr株式会社 Photosensitive resin composition, method for forming resist pattern, method for producing plating molded article, and semiconductor device
CN112694555A (en) * 2020-12-25 2021-04-23 苏州禾川化学技术服务有限公司 Deep ultraviolet positive photoresist film-forming resin and preparation method thereof
CN113234194A (en) * 2021-06-29 2021-08-10 北京科华微电子材料有限公司 Copolymer, primer composition, double-layer system and application of double-layer system in double-layer stripping process
CN113717314A (en) * 2021-08-26 2021-11-30 江苏集萃光敏电子材料研究所有限公司 Photosensitive film-forming resin, photoresist composition and preparation method thereof
CN114133483A (en) * 2021-12-16 2022-03-04 四川华造宏材科技有限公司 Acrylate film forming resin containing adamantane structure, photoresist and preparation method
CN114874384A (en) * 2022-01-21 2022-08-09 南通林格橡塑制品有限公司 193nm photoresist film-forming resin, preparation method thereof and positive photoresist composition

Patent Citations (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63154712A (en) * 1986-12-17 1988-06-28 Japan Synthetic Rubber Co Ltd Production of transparent heat-resistant resin
JP2000204126A (en) * 1999-01-14 2000-07-25 Nippon Shokubai Co Ltd New maleimide-based copolymer
JP2002323771A (en) * 2001-02-22 2002-11-08 Nissan Chem Ind Ltd Composition for forming antireflection film for lithography
KR20050029420A (en) * 2003-09-22 2005-03-28 한국과학기술연구원 A thermally crosslinkable polymer for a bottom anti-reflective coating for photolithography, a composition for preparing a bottom anti-reflective coating using the same, and preparation method thereof
CN103229101A (en) * 2010-11-30 2013-07-31 日产化学工业株式会社 Photosensitive resin composition for microlenses
CN104040432A (en) * 2012-01-19 2014-09-10 日产化学工业株式会社 Negative photosensitive resin composition
CN104641294A (en) * 2012-10-02 2015-05-20 日产化学工业株式会社 Negative photosensitive resin composition
CN107003607A (en) * 2014-12-04 2017-08-01 日产化学工业株式会社 Positive type photosensitive organic compound
CN104650281A (en) * 2014-12-26 2015-05-27 北京鼎材科技有限公司 Alkali-soluble resin polymer for color light filter and light-sensitive resin composition
CN106324985A (en) * 2015-06-30 2017-01-11 东友精细化工有限公司 Colored photosensitive resin composition, color filter and liquid crystal display device
CN111886545A (en) * 2018-03-29 2020-11-03 太阳油墨制造株式会社 Photocurable/thermosetting resin composition, dry film, cured product, and printed wiring board
CN112534352A (en) * 2018-08-21 2021-03-19 Jsr株式会社 Photosensitive resin composition, method for forming resist pattern, method for producing plating molded article, and semiconductor device
CN111234094A (en) * 2018-11-28 2020-06-05 北京鼎材科技有限公司 Modified dye, photosensitive resin composition containing same and application
CN111944090A (en) * 2019-06-06 2020-11-17 上海函泰电子科技有限公司 Polymer resin and preparation method and application thereof
CN112694555A (en) * 2020-12-25 2021-04-23 苏州禾川化学技术服务有限公司 Deep ultraviolet positive photoresist film-forming resin and preparation method thereof
CN113234194A (en) * 2021-06-29 2021-08-10 北京科华微电子材料有限公司 Copolymer, primer composition, double-layer system and application of double-layer system in double-layer stripping process
CN113717314A (en) * 2021-08-26 2021-11-30 江苏集萃光敏电子材料研究所有限公司 Photosensitive film-forming resin, photoresist composition and preparation method thereof
CN114133483A (en) * 2021-12-16 2022-03-04 四川华造宏材科技有限公司 Acrylate film forming resin containing adamantane structure, photoresist and preparation method
CN114874384A (en) * 2022-01-21 2022-08-09 南通林格橡塑制品有限公司 193nm photoresist film-forming resin, preparation method thereof and positive photoresist composition

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
248 nm深紫外光刻胶用成膜树脂的研究进展;魏孜博;马文超;邱迎昕;;影像科学与光化学;第38卷(第3期);第430-435页 *
洪啸吟.《光照下的缤纷世界—光敏高分子化学的应用》.湖南教育出版社,1999,(第1版),第124-126页. *

Also Published As

Publication number Publication date
CN115160495A (en) 2022-10-11

Similar Documents

Publication Publication Date Title
KR100252546B1 (en) Polymer resin and method for preparing the same
CN1478800A (en) Photoetch resist copolymer
KR100395183B1 (en) Polymer having diol structure and negative photoresist composition and pattern forming method using the same
US6403281B1 (en) Cross-linker monomer comprising double bond and photoresist copolymer containing the same
JP3228193B2 (en) Negative photoresist composition and pattern forming method using the same
CN115160495B (en) Photoresist film-forming resin containing maleimide structure and preparation method thereof
JP3869166B2 (en) Photoresist monomer and production method thereof, photoresist copolymer and production method thereof, photoresist composition, photoresist pattern formation method, and semiconductor element
KR100334387B1 (en) Copolymer and manufacturing method thereof and photoresist using the copolymer
JP2008045125A (en) Photosensitive polymer for extreme ultraviolet ray and deep ultraviolet ray and photoresist composition containing the same
KR20000047041A (en) Photoresist crosslinking monomer, polymer thereof and photoresist composition using the same
CN113214427A (en) Bio-based ArF photoresist film-forming resin, photoresist composition and preparation method thereof
JP5021282B2 (en) Copolymer containing structural unit having 3,4-epoxytricyclo [5.2.1.02,6] decane ring and process for producing the same
JP3536015B2 (en) Photoresist monomer and method for producing the same, copolymer for photoresist and method for producing the same, photoresist composition, method for forming photoresist pattern, and semiconductor device
JP3943445B2 (en) Photoresist polymer and photoresist composition
JP3641748B2 (en) Photoresist monomer, photoresist polymer, method for producing photoresist polymer, photoresist composition, method for forming photoresist pattern, and semiconductor element
US6818376B2 (en) Cross-linker monomer comprising double bond and photoresist copolymer containing the same
US20030211734A1 (en) Resist resin, chemical amplification type resist, and method of forming of pattern with the same
JPH1115159A (en) Negative photoresist material and pattern forming method by using same
CN115494697A (en) Chemically amplified photoresist and preparation and use method thereof
JP3058126B2 (en) Photosensitive film composition, photosensitive film composition manufacturing method, and photosensitive film pattern forming method
JP2847413B2 (en) Resist material
Guo et al. Design, synthesis, and photosensitive performance of polymethacrylate‐positive photoresist‐bearing o‐nitrobenzyl group
KR20030002482A (en) Photoresist monomer, polymer thereof and photoresist composition containing it
JP2004002769A (en) Polymer and its production process
KR100362935B1 (en) Novel Photoresist Polymers and Photoresist Compositions Using Them

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant