CN111302959A - Acid diffusion inhibitor with ester bond, preparation method thereof and photoresist composition - Google Patents

Acid diffusion inhibitor with ester bond, preparation method thereof and photoresist composition Download PDF

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CN111302959A
CN111302959A CN202010128579.5A CN202010128579A CN111302959A CN 111302959 A CN111302959 A CN 111302959A CN 202010128579 A CN202010128579 A CN 202010128579A CN 111302959 A CN111302959 A CN 111302959A
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ester bond
acid diffusion
acid
methyl
diffusion inhibitor
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Inventor
顾大公
齐国强
陈玲
马潇
毛智彪
许从应
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Jiangsu Nata Opto Electronic Material Co Ltd
Ningbo Nata Opto Electronic Material Co Ltd
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Ningbo Nata Opto Electronic Material Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C219/00—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C219/02—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C219/04—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C219/06—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having the hydroxy groups esterified by carboxylic acids having the esterifying carboxyl groups bound to hydrogen atoms or to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/08—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions not involving the formation of amino groups, hydroxy groups or etherified or esterified hydroxy groups
    • 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
    • C08F120/00—Homopolymers 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
    • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F120/10—Esters
    • C08F120/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (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
    • 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
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition

Abstract

The invention belongs to the technical field of high molecular polymers, and provides an acid diffusion inhibitor with ester bonds, which takes (methyl) acrylate as a structural unit, and introduces a polymer resin formed by alkaline groups containing ester bonds into the structural unit, thereby avoiding the problems of poor film forming capability, brittle fracture, peeling and the like of a photoresist film caused by the mismatching of the intersolubility between a high molecular resin compound and a micromolecular acid inhibitor in the photoresist, and controlling the photo-acid diffusion of a non-exposure area; meanwhile, the solubility and distribution of the photoresist can be effectively improved, the resolution and line width roughness of the photoresist are improved, and the film forming capability of the photoresist is improved. The invention also provides a preparation method of the acid diffusion inhibitor with ester bond and a photoresist composition thereof. When the acid diffusion inhibitor provided by the invention is applied to a photoresist composition, the acid diffusion inhibitor has the characteristics of fixed distribution, high acid diffusion inhibition capability, matching with the acid active resin in properties and good film forming capability.

Description

Acid diffusion inhibitor with ester bond, preparation method thereof and photoresist composition
Technical Field
The invention belongs to the technical field of high molecular polymers, and particularly relates to an acid diffusion inhibitor with ester bonds, a preparation method thereof and a photoresist composition.
Background
Three important parameters of the photoresist include resolution, sensitivity, and line width roughness, which determine the process window of the photoresist during chip fabrication. With the increasing performance of semiconductor chips, the integration level of integrated circuits is increased exponentially, and the patterns in the integrated circuits are continuously reduced. In order to make patterns of smaller size, the above three performance criteria of the photoresist must be improved. The use of a short wavelength light source in a photolithography process can improve the resolution of the photoresist according to the rayleigh equation. The light source wavelength for the lithographic process has evolved from 365nm (I-line) to 248nm (KrF), 193nm (ArF), 13nm (EUV). In order to improve the sensitivity of the photoresist, the current KrF, ArF and EUV photoresists are mainly made of chemically amplified photosensitive resin.
Studies have shown that controlling photoacid diffusion after exposure of chemically amplified resists is an important means to improve resolution and reduce line width roughness. One of the ways to improve the ability to control photoacid diffusion is to use basic compounds, known as acid diffusion inhibitors, to reduce the photoacid diffusion range by using the principle of acid-base neutralization.
Acid-reactive resins, photosensitizers, acid diffusion inhibitors are the main components in the photoresist formulation. In the prior art, amine molecules are one of the key components for controlling acid diffusion. However, the difference between the amine molecules and the photoresist resin is large in structure, so that the amine molecules cannot be uniformly distributed in the photoresist film, and the resolution and the line width roughness of the photoresist are reduced. On the other hand, in order to achieve better etching resistance, a large number of benzene rings or bulky non-aromatic bridged ring structures are used in the photoresist resin. These structures easily lead to the mutual solubility mismatch between the high molecular compounds, the film forming ability is poor, and the problems of brittle fracture, peeling and the like of the photoresist film occur. Meanwhile, when the micromolecular alkaline compound is applied to an immersion lithography process, the possibility of polluting a photoresist lens exists, and serious consequences are caused.
Therefore, the development of an acid diffusion inhibitor which has fixed distribution, high acid diffusion inhibition capability, matched property with acid-active resin and good film forming capability is imperative, and provides a necessary foundation for the development of the subsequent immersion photoresist.
Disclosure of Invention
The embodiment of the invention provides an acid diffusion inhibitor with ester bonds, aiming at solving the problems of mismatching of intersolubility between high molecular compounds, poor film forming capability, brittle fracture, peeling and the like of a photoresist film. When the acid diffusion inhibitor with the ester bond is applied to the photoresist composition, the acid diffusion inhibitor has the characteristics of fixed distribution, high acid diffusion inhibition capacity, matching with the acid active resin in properties and good film forming capacity.
The embodiment of the invention is realized by that the acid diffusion inhibitor with ester bond has the structural general formula (I) or (II):
Figure BDA0002395170310000021
wherein n is an integer of 2-30, and the weight average molecular weight of the acid diffusion inhibitor with ester bond is 100-30000 g/mol; n isaA carbon chain containing an ether bond and having 1 to 20 carbon atoms; r1One or more of alkyl with 1-20 hydrogen atoms and 1-20 carbon atoms, aryl or substituent containing sulfur/oxygen/nitrogen heteroatom; r2Is one or more of alkyl with 1-20 hydrogen atoms and 1-20 carbon atoms, aryl or substituent containing sulfur/oxygen/nitrogen heteroatom.
In the present application, an acid diffusion inhibitor film-forming resin is formed by introducing an ester bond-containing basic monomer in addition to a (meth) acrylate. Because the basic group is fixed on the high molecular resin structure, and the structure is similar to that of the acid active resin; meanwhile, ester bonds in the structure can improve the solubility of polymer molecules in a solvent, so that the acid inhibitor can be uniformly distributed in the photoresist film. The resin has excellent photoacid diffusion inhibition capability, and improves the resolution and line width roughness of the photoresist; reduce the water solubility of the photoresist components, improve the film forming capability of the photoresist and avoid the contamination of the lens of the photoetching machine.
Further, said R1、R2Is one or more of linear alkyl, cycloalkyl or aryl.
Further, said R1、R2And a nitrogen-containing functional group consisting of N atoms (i.e., R in the above-mentioned general structural formula (I) or (II))1、R2And N atom) is one or at least two of N-butylamino, tert-butylamino, dimethylamino, diethylamino, di-N-propyl, diisopropylamino, di-N-butylamino, di-isobutylamino, di-tert-butylamino, cyclopentylamino, cyclohexylamino, phenylmethylamino, phenylethylamino, phenyl-N-propylamino, phenyl-N-butylamino, phenyl-tert-butylamino, diphenylamino, di (p-methoxyphenyl) amino and di (p-tert-butoxyphenyl) amino.
Further, said R1、R2And a nitrogen-containing functional group consisting of N atoms (i.e., R in the above-mentioned general structural formula (I) or (II))1、R2And a nitrogen-containing functional group consisting of N atoms) is one of the following structures:
Figure BDA0002395170310000031
Figure BDA0002395170310000041
Figure BDA0002395170310000051
the embodiment of the invention also provides a preparation method of the acid diffusion inhibitor with ester bond, the acid diffusion inhibitor with ester bond is prepared by heating and copolymerizing (methyl) acrylate monomer consisting of basic groups containing ester bond in the presence of a free radical initiator, and the preparation method specifically comprises the following steps:
(1) dissolving an alkaline (methyl) acrylate monomer containing ester bonds in a first solvent, and heating to 40-90 ℃ to obtain a mixed solution; the molar ratio of the ester bond-containing basic (meth) acrylate monomer to the first solvent is 1: (4-16);
(2) dissolving an initiator in a second solvent to obtain an initiator solution; the mass of the initiator is 0.3-15% of the mass of the ester bond-containing basic (meth) acrylate monomer, and the molar ratio of the initiator to the second solvent is 1: (4-16);
(3) and (3) adding the initiator solution obtained in the step (2) into the mixed solution obtained in the step (1), carrying out reflux reaction at the constant temperature of 40-90 ℃ for 2-30 hours, cooling to room temperature, precipitating resin by using a non-polar solvent, filtering, and drying to obtain the acid diffusion inhibitor with ester bonds.
Further, in the present invention,
the initiator is one or at least two of azobisisobutyronitrile, azobisisoheptonitrile, tert-butyl peroxypivalate, tert-butyl hydroperoxide, benzoic acid hydroperoxide or benzoyl peroxide;
the first solvent/the second solvent is one or at least two of methanol, ethanol, dioxane, acetone, methyl ethyl ketone, tetrahydrofuran, methyl tetrahydrofuran, benzene, toluene, xylene, chloroform, dichloroethane or trichloroethane;
the nonpolar solvent is one or at least two of pure water, methanol/water mixture, ethanol/water mixture, isopropanol/water mixture, n-heptane, n-hexane, cyclohexane, n-pentane, petroleum ether, diethyl ether or methyl tert-butyl ether;
the structural general formula of the ester bond-containing basic (methyl) acrylate monomer is (III) or (IV):
Figure BDA0002395170310000061
wherein n isbIs a carbon chain containing an ester bond and having 1 to 20 carbon atoms.
Further, the structural formula of the ester bond-containing basic (meth) acrylate monomer is one of the following structures:
Figure BDA0002395170310000062
Figure BDA0002395170310000071
Figure BDA0002395170310000081
Figure BDA0002395170310000091
Figure BDA0002395170310000101
Figure BDA0002395170310000111
Figure BDA0002395170310000121
further, the ester bond-containing basic (meth) acrylate monomer is prepared by:
(1) mixing an alkaline long-chain compound containing ester bonds, an acid-binding agent and a third solvent to obtain a mixed solution, and heating the mixed solution to-20-80 ℃; the molar ratio of the basic long-chain compound containing ester bonds, the acid-binding agent and the third solvent is 1: (1-1.5): (4-16);
(2) dropwise adding (methyl) acryloyl chloride at-20-80 ℃ while stirring, wherein the dropwise adding time is 1-5 h, after the dropwise adding is finished, continuously reacting at-20-80 ℃ for 2-20 h, and then adjusting the temperature to room temperature to obtain a reaction solution; the molar ratio of the basic long-chain compound containing an ester bond to the (meth) acryloyl chloride is 1: (1-1.2);
(3) and (3) washing the reaction solution in the step (2) by using a sodium carbonate aqueous solution, pure water and saturated saline solution in sequence, drying by using anhydrous sodium sulfate, filtering, concentrating the filtrate, and distilling to obtain the alkaline (methyl) acrylate monomer containing the ester bond.
Further, the third solvent is one or at least two of ethyl acetate, butyl acetate, neopentyl acetate, ethyl lactate, propylene glycol methyl ether acetate, propylene glycol mono-acetate ether, propylene glycol monoethyl ether, propylene glycol methyl ether acetate, diethylene glycol methyl ether, diethylene glycol diethyl ether, tetrahydrofuran, methyl tetrahydrofuran, chloroform, dichloromethane, 1, 2-dichloroethane, n-hexane, n-pentane, n-heptane, acetone, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, p-xylene, or biphenyl.
The present embodiment also provides a photoresist composition comprising the acid diffusion inhibitor with an ester bond.
Still further, the photoresist composition further comprises other acid inhibitors.
The other acid inhibitor is one or at least two of N-butylamine, tert-butylamine, dimethylamine, diethylamine, di-N-propylamine, diisopropylamine, di-N-butylamine, diisobutylamine, di-tert-butylamine, trimethylamine, triethylamine, tri-N-propylamine, triisopropylamine, tri-tert-butylamine, ethanolamine, diethanolamine, triethanolamine, cyclopentylamine, cyclohexylamine, morpholine, N-methylcyclopentylamine, methylaniline, ethylaniline, N-butylaniline, tert-butylaniline, dimethylaniline, diethylaniline, dibutylbenzene, and diphenylaniline.
Compared with the prior art, the invention has the following advantages:
(1) the present invention provides an acid diffusion inhibitor in the form of a polymer. It can also control photoacid diffusion in the non-exposed region as well as conventional acid diffusion inhibitors; meanwhile, the method is different from other small molecular organic bases, and ester bonds are introduced into the structure of the flexible long chain. Compared with a carbon chain, the ester chain has better solubility, can more effectively improve the distribution of the ester chain in the photoresist, improve the resolution and line width roughness of the photoresist and improve the film forming capability of the photoresist.
(2) Compared with organic alkali inhibitors, the acid diffusion inhibitor existing in a polymer form has lower solubility in water, and the resin acid diffusion inhibitor can reduce the leaching rate of photoresist and avoid the lens of a photoetching machine from being contaminated when the resin acid diffusion inhibitor is used for immersion photoetching.
Drawings
The invention will be further described with reference to the accompanying drawings and examples, in which:
FIG. 1 is an electron micrograph of a photoresist composition provided in example III of the present invention after photolithography.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In the application, the initiator is an azo initiator, a radical initiator of peroxide, preferably the azo initiator is azobisisobutyronitrile or azobisisoheptonitrile, and preferably the radical initiator of peroxide is tert-butyl peroxypivalate, tert-butyl hydroperoxide, benzoic acid hydroperoxide or benzoyl peroxide, etc.; the amount of the initiator is 0.3 to 15 percent of the total mass of the comonomer; the initiator is added by firstly adding the monomer and part of the solvent, then heating to the polymerization temperature, and then dropwise adding the initiator solution. The temperature of the polymerization reaction is controlled to be between 40 and 90 ℃ according to different solvents and initiators, and the polymerization time is controlled to be between 2 and 30 hours according to different solvents and initiators.
The copolymerization of the acid diffusion inhibitor film-forming resin may be carried out in various solvents or a mixture of solvents including methanol, ethanol, dioxane, acetone, methyl ethyl ketone, tetrahydrofuran, methyl tetrahydrofuran, benzene, toluene, xylene, chloroform, dichloroethane, trichloroethane, etc.
After the copolymerization reaction of the acid diffusion inhibitor film-forming resin is finished, the copolymer can be precipitated and separated in organic or inorganic solvents such as pure water, methanol/water mixture, ethanol/water mixture, isopropanol/water mixture, n-heptane, n-hexane, cyclohexane, n-pentane, petroleum ether, diethyl ether, methyl tert-butyl ether and the like, and the yield of the copolymer after vacuum drying is 60-90%.
The acid diffusion inhibitor can be used for preparing a photoresist composition, and the photoresist composition at least comprises an acid diffusion inhibitor, a film-forming resin with acid activity, a photosensitizer and an organic solvent, wherein the acid diffusion inhibitor is the polymer resin which takes (methyl) acrylate as a structural unit and is formed by introducing basic groups into the (methyl) acrylate; in order to improve the effect, other acid inhibitors can be added for combined use.
The composition comprises, by mass, 0.001-10% of an acid diffusion inhibitor, 1-20% of a film-forming resin having acid activity, 0.01-10% of a photosensitizer, and the balance of an organic solvent.
The preparation method of the photoresist composition comprises the following steps: at room temperature, sequentially adding acid active resin, photosensitizer, acid inhibitor resin and solvent according to a formula ratio into a clean glass bottle, and shaking the mixture in the bottle in a dark place for 16-96 hours to fully dissolve the mixture; then filtering the photoresist solution by using a filter made of a nylon material with the diameter of 0.5 micron or less and a filter made of a UPE material; the filtrate was collected in a clean glass bottle to obtain the desired photoresist composition. After completion, photolithography experiments were performed.
The acid-reactive resin is polymerized by a plurality of functional groups and comprises acid-reactive groups and polar groups. The structural general formula of the acid-reactive resin is as follows:
Figure BDA0002395170310000161
the molecular weight of the acid active film-forming resin is 3000-100000, and the molecular weight is distributed between 1.0-3.0. Wherein the content of acid active group monomer is 30-70%, and the content of polar group monomer is 70-30%. Preferably 50: 50.
the acid-reactive resin contains acid-sensitive groups with different substituents, specifically acid-reactive (methyl) acrylate, and the structure of the acid-reactive resin is at least one monomer in accordance with the chemical general formula, and the specific structural general formula of the acid-reactive monomer is as follows:
Figure BDA0002395170310000162
wherein R isaH, or a carbon chain having 1 to 20 carbon atoms; rbAcid sensitive quaternary carbons.
Specifically, RbThe derivative is a quaternary ester with 6-30 carbon atoms, all hydrogen atoms of carbon atoms connected with ester bond oxygen atoms are substituted by other groups, and possible structures of the derivative are one or more of tert-butyl ester, substituted tert-butyl ester, alkyl substituted adamantyl derivative ester, alkyl substituted norbornyl derivative ester, alkyl substituted cyclic alkyl derivative ester and the like.
The acid-activated resin contains 1 or more polar groups, specifically (methyl) acrylate containing the polar groups, and the structure of the acid-activated resin is at least one monomer in accordance with the chemical general formula, and the specific structural general formula of the polar monomer is as follows:
Figure BDA0002395170310000171
wherein R iscH, or a carbon chain having 1 to 20 carbon atoms; rdA polar group-containing (meth) acrylate.
Specifically, RdThe compound is a cyclic, cage-shaped or straight-chain carbon-containing structure containing hydroxyl groups with the carbon number of 6-30 and various lactone structures, and possible structures of the compound are adamantyl ester containing 1 or more independent hydroxyl groups, cyclohexyl ester containing 1 or more independent hydroxyl groups, cyclopentyl ester containing 1 or more independent hydroxyl groups, and lactone structures containing 1 or more independent hydroxyl groups
The lactone compound comprises one or more of polycyclic ester compounds with one or more independent hydroxyl groups, caged ester compounds with 1 or more independent hydroxyl groups, butyrolactone, valerolactone, substituted valerolactone, caprolactone, substituted caprolactone, lactone containing adamantane structure, lactone containing polycyclic structure, lactone containing caged structure and the like.
The preparation method of the acid active film-forming resin comprises the following steps: the comonomer is prepared by polymerization reaction in a solvent in the presence of a free radical initiator. In the polymerization reaction of the acid-active film-forming resin, the initiator is an azo initiator and a radical initiator of peroxide, the preferable azo initiator is azobisisobutyronitrile or azobisisoheptonitrile, and the preferable radical initiator of the peroxide is tert-butyl peroxypivalate, tert-butyl hydroperoxide, benzoic acid hydroperoxide or benzoyl peroxide and the like; the amount of the initiator is 0.3 to 15 percent of the total mass of the comonomer; the initiator is added by firstly adding the monomer and part of the solvent, then heating to the polymerization temperature, and then dropwise adding the initiator solution. The temperature of the polymerization reaction is controlled to be between 40 and 90 ℃ according to different solvents and initiators, and the polymerization time is controlled to be between 4 and 32 hours according to different solvents and initiators.
The copolymerization of the acid-reactive film-forming resin may be carried out in a variety of solvents or mixtures of solvents including methanol, ethanol, dioxane, acetone, methyl ethyl ketone, tetrahydrofuran, methyl tetrahydrofuran, benzene, toluene, xylene, chloroform, dichloroethane, trichloroethane, and the like.
After the copolymerization reaction of the acid active film-forming resin is finished, the copolymer can be precipitated and separated in organic or inorganic solvents such as pure water, methanol/water mixture, ethanol/water mixture, isopropanol/water mixture, n-heptane, n-hexane, cyclohexane, n-pentane, petroleum ether, diethyl ether, methyl tert-butyl ether and the like, and the yield of the copolymer after vacuum drying is 50-80%.
The acid diffusion inhibitor is a nitrogen-containing compound, including primary amine, secondary amine and tertiary amine compounds, especially amine compounds having hydroxyl, ether bond, ester bond, amide bond, lactone ring, cyano or sulfonate ester bond, and may be one or more of aliphatic or aromatic amines such as diethylamine, triethylamine, ethanolamine, triethanolamine, aniline, phenethylamine, etc.
The organic solvent capable of dissolving the acid active resin, the flexible long-chain polysulfide salt photo-acid generator and the acid diffusion inhibitor is one or more of propylene glycol methyl ether acetate, propylene glycol monoacetate, propylene glycol monoethyl ether, propylene glycol methyl ether acetate, diethylene glycol methyl ether, diethylene glycol diethyl ether, butyl acetate, neopentyl acetate, ethyl lactate, methyl ethyl ketone, cyclohexanone and methyl isobutyl ketone.
The acid diffusion inhibitor with ester bonds is prepared by heating (methyl) acrylate monomer consisting of basic groups containing ester bonds for copolymerization reaction in the presence of a free radical initiator, and specifically comprises the following steps:
(1) dissolving an alkaline (methyl) acrylate monomer containing ester bonds in a first solvent, and heating to 40-90 ℃ to obtain a mixed solution; the molar ratio of the ester bond-containing basic (meth) acrylate monomer to the first solvent is 1: (4-16);
(2) dissolving an initiator in a second solvent to obtain an initiator solution; the mass of the initiator is 0.3-15% of the mass of the ester bond-containing basic (meth) acrylate monomer, and the molar ratio of the initiator to the second solvent is 1: (4-16);
(3) and (3) adding the initiator solution obtained in the step (2) into the mixed solution obtained in the step (1), carrying out reflux reaction at the constant temperature of 40-90 ℃ for 2-30 hours, cooling to room temperature, precipitating resin by using a non-polar solvent, filtering, and drying to obtain the acid diffusion inhibitor with ester bonds.
The ester bond-containing basic (meth) acrylate monomer is prepared by the following method:
(1) mixing an alkaline long-chain compound containing ester bonds, an acid-binding agent and a third solvent to obtain a mixed solution, and heating the mixed solution to-20-80 ℃; the molar ratio of the basic long-chain compound containing ester bonds, the acid-binding agent and the third solvent is 1: (1-1.5): (4-16);
(2) dropwise adding (methyl) acryloyl chloride at-20-80 ℃ while stirring, wherein the dropwise adding time is 1-5 h, after the dropwise adding is finished, continuously reacting at-20-80 ℃ for 2-20 h, and then adjusting the temperature to room temperature to obtain a reaction solution; the molar ratio of the basic long-chain compound containing an ester bond to the (meth) acryloyl chloride is 1: (1-1.2);
(3) and (3) washing the reaction solution in the step (2) by using a sodium carbonate aqueous solution, pure water and saturated saline solution in sequence, drying by using anhydrous sodium sulfate, filtering, concentrating the filtrate, and distilling to obtain the alkaline (methyl) acrylate monomer containing the ester bond.
Example one
Preparation of a (meth) acrylate having a basic group:
Figure BDA0002395170310000191
the preparation method comprises the following steps: in a round-bottomed flask equipped with a cooling, 20g of a basic long-chain compound having an ester bond, 13g of triethylamine and 150g of dichloromethane were added, and the mixture was cooled to 0 ℃. Then, 11g of (meth) acryloyl chloride was added dropwise with stirring, and a large amount of solid was precipitated. After the addition was complete, stirring was continued for 2 h. Then slowly raising the reaction liquid to room temperature, and washing for 2 times by using saturated sodium carbonate aqueous solution, wherein each time is 200 mL; washing with 150mL of pure water for 2 times; finally, 150mL of saturated saline was washed once. The organic phase was dried over anhydrous sodium sulfate, concentrated and distilled to give 25g N, N-dimethylethanol (meth) acrylate in 82% yield. Nuclear magnetic results:1H NMR(CDCl3，δ)2.11，s，3H；2.90，s，6H；2.63-2.75，m，4H；3.31，m，2H；4.30-4.41，m，6H；5.5，s，1H；6.5，s，1H。
example two
An acid diffusion inhibitor with ester bonds is prepared by carrying out copolymerization reaction on the following comonomers by heating in the presence of a free radical initiator:
Figure BDA0002395170310000201
the preparation method comprises the following steps: a500 mL four-necked flask equipped with a magnetic stirrer with a heater, a condenser tube, and a thermometer was charged with 50g of an alkaline methacrylic acid monomer and 300g of methyl ethyl ketone, stirred under nitrogen for 10 minutes, and then heated to 65 to 70 ℃. Then dropwise adding 2.5g of Azodiisobutyronitrile (AIBN) and 50g of methyl ethyl ketone solution into the reaction system within 10 minutes, continuing to react and reflux for 8-12 hours after the addition is finished, and then cooling to room temperature to obtain a mixture; and placing the mixture in electronic grade n-hexane for precipitation and suction filtration, taking filter residue, dissolving the filter residue with 200g of electronic grade acetone, placing the filter residue in electronic grade n-hexane again for precipitation, filtering, taking the filter residue, and drying to obtain polymer solid, namely the acid diffusion inhibitor with ester bonds, wherein the yield is 68%, the molecular weight is 7254, and the molecular weight distribution is 2.12.
EXAMPLE III
This example is an application example of the present invention, which prepares a positive chemically amplified photoresist containing acid diffusion inhibitor resin, and the formulation thereof is as follows:
the acid diffusion inhibitor resin was the resin in example two.
The acid-reactive resin comprises 2 acid-reactive groups and 2 polar groups in a ratio of 50: 50.
the photosensitizer is perfluorobutyl sulfonic acid triphenyl sulfonium salt.
The solvent was PGMEA: cyclohexanone ═ 7: 3.
the preparation method of the specific formula comprises the following steps:
in a new clean 100mL glass bottle, add 8.5g acid active resin, 0.21g perfluorobutyl sulfonic acid triphenyl sulfonium salt, 0.06g acid diffusion inhibitor resin, 63g PGMEA, 27g cyclohexanone. The mixture was shaken in a bottle for 24 hours at room temperature to dissolve it sufficiently. The photoresist solution was then filtered through 0.22 micron and 0.02 micron filters, respectively. After completion, photolithography experiments were performed.
The photoetching experimental method comprises the following steps: the prepared photoresist is formed into a film on a 12' silicon wafer in a rotating mode at the speed of 2000-3000 r/min, baked for 90 seconds on a hot plate at the temperature of 120 ℃, and then exposed on an exposure machine, wherein the exposure intensity is 10-50mJ/cm2. After exposure, baking the substrate on a hot plate at 110 ℃ for 90 seconds, finally developing the substrate in 2.38% TMAH developer for 60 seconds, drying the substrate, and detecting the photoetching result on an electron microscope, wherein the experimental result is shown in figure 1.
The acid diffusion inhibitor resin with ester bonds is a high-molecular acid inhibitor, and can well control the photoacid diffusion of a non-exposure area; meanwhile, the coating is well distributed in the photoresist, is not easy to separate out in lens liquid, and has good application prospect in an ArF photoresist formula.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.

Claims (10)

1. An acid diffusion inhibitor having an ester bond, characterized in that it has a general structural formula (I) or (II):
Figure FDA0002395170300000011
wherein n is an integer of 2-30, and the weight average molecular weight of the acid diffusion inhibitor with ester bond is 100-30000 g/mol; n isaIs a carbon chain containing ester bonds and having 1-20 carbon atoms; r1One or more of alkyl with 1-20 hydrogen atoms and 1-20 carbon atoms, aryl or substituent containing sulfur/oxygen/nitrogen heteroatom; r2Is one or more of alkyl with 1-20 hydrogen atoms and 1-20 carbon atoms, aryl or substituent containing sulfur/oxygen/nitrogen heteroatom.
2. The acid diffusion inhibitor with ester linkage of claim 1Formulation characterized in that said R is1、R2Is one or more of linear alkyl, cycloalkyl or aryl.
3. The acid diffusion inhibitor with ester bond according to claim 1, wherein R is1、R2And the structure of the nitrogen-containing functional group consisting of N atoms is one of the following structures:
Figure FDA0002395170300000012
Figure FDA0002395170300000021
Figure FDA0002395170300000031
4. the method for producing an acid diffusion inhibitor having an ester bond according to any one of claims 1 to 3, which comprises the steps of:
(1) dissolving an alkaline (methyl) acrylate monomer containing ester bonds in a first solvent, and heating to 40-90 ℃ to obtain a mixed solution; the molar ratio of the ester bond-containing basic (meth) acrylate monomer to the first solvent is 1: (4-16);
(2) dissolving an initiator in a second solvent to obtain an initiator solution; the mass of the initiator is 0.3-15% of the mass of the ester bond-containing basic (meth) acrylate monomer, and the molar ratio of the initiator to the second solvent is 1: (4-16);
(3) and (3) adding the initiator solution obtained in the step (2) into the mixed solution obtained in the step (1), carrying out reflux reaction at the constant temperature of 40-90 ℃ for 2-30 hours, cooling to room temperature, precipitating resin by using a non-polar solvent, filtering, and drying to obtain the acid diffusion inhibitor with ester bonds.
5. The method for producing an acid diffusion inhibitor having an ester bond according to claim 4,
the initiator is one or at least two of azobisisobutyronitrile, azobisisoheptonitrile, tert-butyl peroxypivalate, tert-butyl hydroperoxide, benzoic acid hydroperoxide or benzoyl peroxide;
the first solvent/the second solvent is one or at least two of methanol, ethanol, dioxane, acetone, methyl ethyl ketone, tetrahydrofuran, methyl tetrahydrofuran, benzene, toluene, xylene, chloroform, dichloroethane or trichloroethane;
the nonpolar solvent is one or at least two of pure water, methanol/water mixture, ethanol/water mixture, isopropanol/water mixture, n-heptane, n-hexane, cyclohexane, n-pentane, petroleum ether, diethyl ether or methyl tert-butyl ether;
the structural general formula of the ester bond-containing basic (methyl) acrylate monomer is (III) or (IV):
Figure FDA0002395170300000041
wherein n isbIs a carbon chain containing an ester bond and having 1 to 20 carbon atoms.
6. The method for preparing an acid diffusion inhibitor having an ester bond according to claim 4, wherein the basic (meth) acrylate monomer having an ester bond has a structural formula of one of the following structures:
Figure FDA0002395170300000051
Figure FDA0002395170300000061
Figure FDA0002395170300000071
Figure FDA0002395170300000081
Figure FDA0002395170300000091
Figure FDA0002395170300000101
Figure FDA0002395170300000111
7. the method for producing an acid diffusion inhibitor having an ester bond according to any one of claims 4 to 6, wherein the ester bond-containing basic (meth) acrylate monomer is produced by:
(1) mixing an alkaline long-chain compound containing ester bonds, an acid-binding agent and a third solvent to obtain a mixed solution, and heating the mixed solution to-20-80 ℃; the molar ratio of the basic long-chain compound containing ester bonds, the acid-binding agent and the third solvent is 1: (1-1.5): (4-16);
(2) dropwise adding (methyl) acryloyl chloride at-20-80 ℃ while stirring, wherein the dropwise adding time is 1-5 h, after the dropwise adding is finished, continuously reacting at-20-80 ℃ for 2-20 h, and then adjusting the temperature to room temperature to obtain a reaction solution; the molar ratio of the basic long-chain compound containing an ester bond to the (meth) acryloyl chloride is 1: (1-1.2);
(3) and (3) washing the reaction solution in the step (2) by using a sodium carbonate aqueous solution, pure water and saturated saline solution in sequence, drying by using anhydrous sodium sulfate, filtering, concentrating the filtrate, and distilling to obtain the alkaline (methyl) acrylate monomer containing the ester bond.
8. The method for producing an acid diffusion inhibitor having an ester bond according to claim 7,
the third solvent is one or at least two of ethyl acetate, butyl acetate, neopentyl acetate, ethyl lactate, propylene glycol methyl ether acetate, propylene glycol monoacetate, propylene glycol monoethyl ether, propylene glycol methyl ether acetate, diethylene glycol methyl ether, diethylene glycol diethyl ether, tetrahydrofuran, methyl tetrahydrofuran, trichloromethane, dichloromethane, 1, 2-dichloroethane, n-hexane, n-pentane, n-heptane, acetone, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, p-xylene or biphenyl.
9. A photoresist composition comprising the acid diffusion inhibitor with ester bond of any one of claims 1-3.
10. The photoresist composition of claim 9, wherein the photoresist composition further comprises an additional acid inhibitor; the other acid inhibitor is one or at least two of N-butylamine, tert-butylamine, dimethylamine, diethylamine, di-N-propylamine, diisopropylamine, di-N-butylamine, diisobutylamine, di-tert-butylamine, trimethylamine, triethylamine, tri-N-propylamine, triisopropylamine, tri-tert-butylamine, ethanolamine, diethanolamine, triethanolamine, cyclopentylamine, cyclohexylamine, morpholine, N-methylcyclopentylamine, methylaniline, ethylaniline, N-butylaniline, tert-butylaniline, dimethylaniline, diethylaniline, dibutylbenzene, and diphenylaniline.
CN202010128579.5A 2020-02-28 2020-02-28 Acid diffusion inhibitor with ester bond, preparation method thereof and photoresist composition Pending CN111302959A (en)

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