CN111285963A - Hydroxyl-containing acid diffusion inhibitor, preparation method thereof and photoresist composition - Google Patents
Hydroxyl-containing acid diffusion inhibitor, preparation method thereof and photoresist composition Download PDFInfo
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- CN111285963A CN111285963A CN202010128247.7A CN202010128247A CN111285963A CN 111285963 A CN111285963 A CN 111285963A CN 202010128247 A CN202010128247 A CN 202010128247A CN 111285963 A CN111285963 A CN 111285963A
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
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Abstract
The invention discloses a hydroxyl-containing acid diffusion inhibitor and a preparation method and application thereof. The structure of the hydroxyl-containing acid diffusion inhibitor is shown as a general formula (I), and the hydroxyl-containing acid diffusion inhibitor contains naAnd the moiety of the hydroxyl structure is a hydroxyl functional unit; comprising R3、R4And nbThe moiety of (a) is a basic functional unit. The hydroxyl-containing acid diffusion inhibitor has good solubility, can effectively improve the distribution of the hydroxyl-containing acid diffusion inhibitor in the photoresist, improves the resolution and line width roughness of the photoresist, and improves the film forming capability of the photoresist. The preparation method has mild reaction conditions and high efficiency. When the hydroxyl-containing acid diffusion inhibitor is applied to a photoresist composition, the hydroxyl-containing acid diffusion inhibitor has fixed distribution and acid diffusionHigh inhibition ability, matching with the acid active resin and good film forming ability.
Description
Technical Field
The invention belongs to the technical field of high molecular polymers, and particularly relates to a hydroxyl-containing acid diffusion inhibitor, 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 invention aims to overcome the defects of the prior art, and provides a hydroxyl-containing acid diffusion inhibitor, a preparation method and application thereof, so as to solve the technical problems of poor film forming capability of a photoresist, brittle fracture, peeling and the like of the photoresist film caused by mismatching of intersolubility between the existing acid diffusion inhibitor and a high molecular compound.
In order to achieve the object, according to one aspect of the present invention, there is provided a hydroxyl group-containing acid diffusion inhibitor. The structural general formula of the hydroxyl-containing acid diffusion inhibitor is shown as the following general formula (I):
wherein R in the general formula (I)1、R2Is H or methyl; r3、R4One or more of alkyl with 1-40 hydrogen atoms and 1-20 carbon atoms, aryl or substituent containing sulfur/oxygen/nitrogen heteroatom; n is 5-200, naIs one or more of an alkyl group, an aryl group, or a functional structure containing a sulfur/oxygen/nitrogen heteroatom; n isbThe carbon chain contains one or more ether bonds and one or more ester bonds, and the number of carbon atoms is 1-20; wherein, n is containedaAnd the moiety of the hydroxyl structure is a hydroxyl functional unit; comprising said R3、R4And nbThe moiety of (a) is a basic functional unit.
In another aspect of the present invention, a method for preparing the hydroxyl group-containing acid diffusion inhibitor of the present invention is provided. The preparation method of the hydroxyl-containing acid diffusion inhibitor comprises the following steps:
dissolving a monomer containing the hydroxyl functional unit and a monomer containing the alkaline functional unit in a first solvent to obtain a mixed solution containing an acid diffusion inhibitor monomer;
dissolving an initiator in a second solvent to obtain an initiator solution;
and mixing the initiator solution and the mixed solution, carrying out constant-temperature reflux polymerization at 40-90 ℃ for 2-30 hours, cooling to room temperature, carrying out separation treatment, and drying to obtain the hydroxyl-containing acid diffusion inhibitor.
In yet another aspect of the present invention, a photoresist composition is provided. The photoresist composition comprises the hydroxyl group-containing acid diffusion inhibitor of the present invention.
Compared with the prior art, the invention has the following advantages:
(1) the hydroxyl-containing acid diffusion inhibitor can control the photo-acid diffusion of the non-exposure area; meanwhile, the method can be distinguished from other small molecular organic bases, and the contained alkaline functional units are better compatible with film-forming resin in a polymer form, so that the line resolution is improved, and the roughness is reduced. In addition, hydroxyl is introduced into the structure of the flexible long chain, so that the photoresist has better solubility, the distribution of the photoresist can be further effectively improved, the resolution and the line width roughness of the photoresist are improved, and the film forming capability of the photoresist is improved. (2) Compared with the traditional organic alkali inhibitor, the acid diffusion inhibitor in the form of polymer 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.
The preparation method of the hydroxyl-containing acid diffusion inhibitor adopts the step of directly mixing the monomer containing the hydroxyl functional unit, the monomer containing the alkaline functional unit and the initiator solution for polymerization reaction, thereby generating the hydroxyl-containing acid diffusion inhibitor simultaneously containing the hydroxyl functional unit and the alkaline functional unit.
The photoresist composition contains the hydroxyl-containing acid diffusion inhibitor, so that the components contained in the photoresist composition are uniformly dispersed, the acid diffusion inhibition capacity is high, the characteristics of the photoresist composition are matched with those of acid active resin, and the film forming capacity is good, so that the stability of the photoetching performance of the photoresist can be ensured, the resolution and the line width roughness of the photoresist are effectively ensured and improved, the film forming capacity is good, and the bad phenomena of brittle fracture, peeling and the like of the photoresist film are effectively avoided.
Drawings
The invention will be further described with reference to the accompanying drawings and examples, in which:
FIG. 1 is a schematic process flow diagram of a method for preparing a hydroxyl-containing acid diffusion inhibitor according to an embodiment of the present invention;
FIG. 2 is an electron micrograph of a photoresist provided in example 2-1 of the present invention after photolithography;
FIG. 3 is an electron micrograph of the photoresist provided in example 2-2 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 one aspect, embodiments of the present invention provide a hydroxyl-containing acid diffusion inhibitor. The structural general formula of the hydroxyl-containing acid diffusion inhibitor is shown as the following general formula (I):
wherein R in the general formula (I)1、R2Is H or methyl;
R3、R4is an alkyl group having 1 to 40 hydrogen atoms and 1 to 20 carbon atoms, an aryl group or a sulfur/oxygen/nitrogen-containing heteroatomOne or more of substituents;
n is 5 to 200; specific examples are positive integers;
nais one or more of an alkyl group, an aryl group, or a functional structure containing a sulfur/oxygen/nitrogen heteroatom;
nbthe carbon chain contains one or more ether bonds and one or more ester bonds and has 1-20 carbon atoms.
Wherein said n contained in said general formula (I)aAnd the moiety of the hydroxyl structure is a hydroxyl functional unit; the R contained therein3、R4And nbThe moiety of (a) is a basic functional unit.
Due to the R contained in the general formula (I)3、R4And nbThe basic functional unit imparts a function of inhibiting photoacid diffusion to the hydroxyl group-containing acid diffusion inhibitor, thereby avoiding pattern exposure transition and obtaining a clear pattern after development. The basic functional unit preferably comprises any one of the following structures:
since n in the general formula (I)aAnd the hydroxyl structure is partially a hydroxyl functional unit, and the hydroxyl functional unit endows the hydroxyl-containing acid diffusion inhibitor with better solubility, can effectively improve the distribution of the acid diffusion inhibitor in the photoresist, improve the resolution and line width roughness of the photoresist and improve the film forming capability of the photoresist. Thus, the hydroxyl functional unit preferably comprises any of the following structures:
wherein n in the molecular structural formula of the hydroxyl functional unitc、nd、neThe data shown are the number of carbon atoms in the carbon chain, e.g. nc3 to 17 represents a carbon chain having 3 to 17 carbon atoms and nd1-6 represents the number of carbon atoms of carbon chain 1-6, ne1 to 6 represent the number of carbon atoms of the carbon chain of 1 to 6. Therefore, on the premise of retaining the acid inhibition function, the hydroxyl functional unit and the alkaline functional unit are introduced into the branched chain of the acid diffusion inhibitor, so that the solubility of the high polymer molecule of the acid diffusion inhibitor in a solvent is improved, and the acid diffusion inhibitor can be uniformly distributed in a photoresist film. The acid diffusion inhibitor with the structure shows excellent photoacid diffusion inhibition capability, so that the resolution and line width roughness of the photoresist are improved, the water solubility of photoresist components is reduced, the film forming capability of the photoresist is improved, and the lens contamination of a photoetching machine is avoided.
On the other hand, the embodiment of the invention also provides a preparation method of the hydroxyl-containing acid diffusion inhibitor based on the hydroxyl-containing acid diffusion inhibitor. The preparation method of the hydroxyl-containing acid diffusion inhibitor has the process flow as shown in figure 1, and comprises the following steps:
s01, preparing a mixed solution containing an acid diffusion inhibitor monomer:
dissolving a monomer containing the hydroxyl functional unit and a monomer containing the alkaline functional unit in a first solvent to obtain a mixed solution containing an acid diffusion inhibitor monomer;
s02: preparing an initiator-containing solution:
dissolving an initiator in a second solvent to obtain an initiator solution;
s03: mixing the mixed solution containing the acid diffusion inhibitor monomer with the solution containing the initiator to carry out polymerization:
and mixing the initiator solution and the mixed solution, carrying out constant-temperature reflux polymerization at 40-90 ℃ for 2-30 hours, cooling to room temperature, carrying out separation treatment, and drying to obtain the hydroxyl-containing acid diffusion inhibitor.
Wherein, in step S01, the hydroxyl functional unit-containing monomer is a hydroxyl functional unit contained in the hydroxyl-containing acid diffusion inhibitor described above. Thus, the monomer containing a hydroxyl functional unit may be a monomer containing n in formula I aboveaAnd a moiety of a hydroxyl structure, preferably a monomer comprising at least one hydroxyl-containing functional unit as shown in structures 143 to 2760 above.
The monomer containing a basic functional unit is a basic functional unit contained in the above-mentioned hydroxyl group-containing acid diffusion inhibitor. Thus, the monomer containing the basic functional unit may be a monomer containing R in formula I above3、R4And nbThe partial structural monomer is preferably a monomer containing at least one basic functional unit represented by structural formulae 1 to 142.
In the embodiment, the monomer containing the hydroxyl functional unit and the monomer containing the basic functional unit are (1-60): (40-99) in the first solvent. The ratio of the hydroxyl-containing functional unit to the basic functional unit in the finally prepared target hydroxyl-containing acid diffusion inhibitor is optimized by adjusting the mixing ratio of the two monomers, so as to further improve the performance of the hydroxyl-containing acid diffusion inhibitor as described above.
In the examples, the first solvent is used in an amount of 1 to 100 times the total mass of the monomers. The amount of the first solvent is controlled to increase the dissolution rate of the monomer, and the concentration of the reaction solution in the step S03 is indirectly controlled to facilitate the generation of the target product and increase the drop rate of the target product.
In addition to the above embodiments, the first solvent is preferably one or at least two of methanol, ethanol, dioxane, acetone, methyl ethyl ketone, tetrahydrofuran, methyl tetrahydrofuran, benzene, toluene, xylene, n-hexane, n-heptane, n-pentane, ethyl acetate, butyl acetate, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, petroleum ether, diethyl ether, n-butyl ether, chloroform, dichloroethane, and trichloroethane. The first solvent can not only improve the solubility of each monomer, but also stabilize the polymerization reaction solvent, improve the polymerization reaction efficiency among the monomers and improve the yield of the hydroxyl-containing acid diffusion inhibitor.
In the step S02, the initiator is preferably mixed according to a ratio that the amount of the second solvent is 1-50 times of the amount of the initiator to prepare an initiator solution. In specific embodiments, the initiator is an azo initiator, a radical initiator of peroxide, preferably azobisisobutyronitrile or azobisisoheptonitrile, and preferably a radical initiator of peroxide is t-butyl peroxypivalate, t-butyl hydroperoxide, benzoic acid hydroperoxide, or benzoyl peroxide. Thus, the initiator may be one or at least two of azobisisobutyronitrile, azobisisoheptonitrile, t-butyl peroxypivalate, t-butyl hydroperoxide, benzoic acid hydroperoxide, or benzoyl peroxide; the second solvent is preferably one or at least two of methanol, ethanol, dioxane, acetone, methyl ethyl ketone, tetrahydrofuran, methyl tetrahydrofuran, benzene, toluene, xylene, n-hexane, n-heptane, n-pentane, ethyl acetate, butyl acetate, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, petroleum ether, diethyl ether, n-butyl ether, chloroform, dichloroethane or trichloroethane.
In the step S03, the initiator solution and the mixed solution are mixed and polymerized in a ratio that the mass of the initiator is 0.3% to 15% of the total mass of the monomers in the mixed solution. Preferably, the mixed solution containing the acid diffusion inhibitor monomer is heated to the polymerization temperature, and then the initiator solution is added dropwise. The temperature of the polymerization reaction is controlled to be between 40 and 90 ℃ according to different used solvents and initiators, and the polymerization reaction time is controlled to be between 2 and 30 hours according to different used solvents and initiators. The solvent for the polymerization reaction is composed of the first solvent and the second solvent.
And (3) separating the mixture after the polymerization reaction is finished to obtain the hydroxyl-containing acid diffusion inhibitor. In an embodiment, the separation treatment may be to mix the mixture after the polymerization reaction in a separation solution so that the hydroxyl group-containing acid diffusion inhibitor is precipitated and separated. In specific embodiments, the separation solution may be 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 drying process for the collected precipitate may be, but is not limited to, a vacuum drying process. The detection shows that the yield of the hydroxyl-containing acid diffusion inhibitor after drying treatment is 60-90%.
The preparation method of the hydroxyl-containing acid diffusion inhibitor is to directly mix the acid diffusion inhibitor-containing monomer solution and the initiator solution for polymerization reaction, so that the hydroxyl-containing acid diffusion inhibitor is generated. In addition, according to the method for preparing the hydroxyl group-containing acid diffusion inhibitor, the step S01 and the step S02 have no inevitable sequence relationship.
In another aspect, based on the hydroxyl-containing acid diffusion inhibitor and the preparation method thereof, the embodiment of the invention also provides a photoresist composition. The photoresist composition at least comprises an acid diffusion inhibitor, a film-forming resin with acid activity, a photosensitizer and an organic solvent. In one embodiment, the acid diffusion inhibitor is 0.001-10%, the film-forming resin with acid activity is 1-20%, the photosensitizer is 0.01-10%, and the balance is organic solvent. Wherein the acid diffusion inhibitor comprises a hydroxyl group-containing acid diffusion inhibitor described above. The acid diffusion inhibitor may also be added with other acid inhibitors, i.e. the hydroxyl-containing acid diffusion inhibitor is used in combination with other acid inhibitors, in order to enhance the action of the acid diffusion inhibitor. In particular embodiments, the other acid inhibitors include one or at least two of N-butylamine, t-butylamine, dimethylamine, diethylamine, di-N-propylamine, diisopropylamine, di-N-butylamine, diisobutylamine, di-t-butylamine, trimethylamine, triethylamine, tri-N-propylamine, triisopropylamine, tri-t-butylamine, ethanolamine, diethanolamine, triethanolamine, cyclopentylamine, cyclohexylamine, morpholine, N-methylcyclopentylamine, methylaniline, ethylaniline, N-butylaniline, t-butylaniline, dimethylaniline, diethylaniline, dibutylbenzene, diphenylaniline.
In the embodiment, the content of the acid diffusion inhibitor in the photoresist composition is 0.001-10% by mass, the content of the film-forming resin with acid activity is 1-20% by mass, the content of the photosensitizer is 0.01-10% by mass, and the balance is 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, and shaking the mixture in a 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 is collected, e.g., in a clean glass vial, to obtain the desired photoresist composition. After completion, photolithography experiments were performed.
The film-forming resin with acid activity in the photoresist composition is formed by polymerizing a plurality of functional groups and comprises an acid active group and a polar group. The structural general formula of the film-forming resin is as follows:
the molecular weight of the 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 film-forming resin contains acid-sensitive groups with different substituents, specifically acid-active (methyl) acrylate, the structure of the acid-active (methyl) acrylate is at least one monomer in accordance with the chemical general formula, and the specific structural general formula of the acid-active monomer is as follows:
wherein R isaH, or a carbon chain having 1 to 20 carbon atoms; rbAcid sensitive quaternary carbons.
Specifically, RbThe compound is a quaternary ester with 6-30 carbon atoms, all hydrogen atoms of carbon atoms connected with hydroxyl oxygen atoms are replaced by other groups, and possible structures of the compound 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 film-forming resin contains 1 or more polar groups, specifically (methyl) acrylate containing the polar groups, and the structure of the film-forming 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:
wherein，RcH, 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 atom number of 6-30 and various lactone structures, and possible structures of the compound are one or more of adamantane 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, polycycle ester compound containing 1 or more independent hydroxyl groups, cage-shaped ester compound containing 1 or more independent hydroxyl groups, butyrolactone, valerolactone, substituted valerolactone, caprolactone, substituted caprolactone, lactone containing a adamantane structure, lactone containing a polycyclic structure, lactone containing a cage-shaped structure and the like.
The film-forming resin can be prepared according to the following preparation method: the comonomer is prepared by polymerization reaction in a solvent in the presence of a free radical initiator. In the polymerization reaction of the film-forming resin, an 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 film-forming resin may be carried out in various 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 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 the hydroxyl-containing acid diffusion inhibitor described above and is not described herein again for brevity.
The organic solvent in the photoresist composition 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. These are organic solvents that are effective to dissolve the other components contained in the photoresist composition.
The photoresist composition contains the hydroxyl-containing acid diffusion inhibitor, so that the photoresist composition has the advantages of uniform distribution, high acid diffusion inhibition capability, matching with acid-active resin in properties and good film forming capability, can ensure stable photoetching performance of the photoresist, and effectively ensures and improves the resolution and line width roughness of the photoresist; and the film forming capability is good, and the bad phenomena of brittle fracture, peeling and the like of the photoresist film are effectively avoided.
The hydroxyl group-containing acid diffusion inhibitor, its preparation method and application will now be described in further detail with reference to specific examples.
The acid diffusion inhibitor containing a hydroxyl group and preparation examples thereof
Examples 1 to 1
This example provides an acid diffusion inhibitor having hydroxyl groups and a method for preparing the same. The structural formula of the hydroxyl-containing acid diffusion inhibitor is as follows:
the preparation method of the hydroxyl-containing acid diffusion inhibitor comprises the following steps:
(1) adding 45g of monomer 1 and 5g of monomer 374 into a reaction kettle filled with nitrogen, adding 60g of first ethyl acetate into the reaction kettle, uniformly stirring, heating the reaction kettle to 77 ℃, dropwise adding (dropwise adding time is 10min) a mixed solution of 10g of second ethyl acetate and 1g of benzoyl peroxide into the reaction kettle, reacting for 7 hours at 77 ℃, stopping reaction, and cooling the temperature of the reaction kettle to room temperature;
(2) adding 600g of first methanol into the reaction kettle cooled to room temperature in the step (1), leading out liquid in the reaction kettle after precipitation is carried out for 1h, and then adding 70g of third ethyl triacetate into the reaction kettle until the precipitate is dissolved;
(3) adding 600g of second methanol into the reaction kettle in the step (2), repeating the operation in the step (2) for 3 times to obtain a solid precipitate, and placing the solid precipitate in vacuum for drying to obtain 37g of resin A; GPC equipment measured the molecular weight Mw of the modified film-forming resin 9269 and the PDI of 1.44.
Examples 1 to 2
This example provides a hydroxyl-containing acid diffusion inhibitor and a method for its preparation. The structural formula of the hydroxyl-containing acid diffusion inhibitor is as follows:
the preparation method of the hydroxyl-containing acid diffusion inhibitor comprises the following steps:
(1) adding 45g of monomer 38 and 5g of monomer 428 into a reaction kettle filled with nitrogen, adding 60g of first ethyl acetate into the reaction kettle, uniformly stirring, heating the reaction kettle to 77 ℃, dropwise adding (dropwise adding time is 10min) a mixed solution of 10g of second ethyl acetate and 1g of benzoyl peroxide into the reaction kettle, reacting for 7 hours at 77 ℃, stopping reaction, and cooling the temperature of the reaction kettle to room temperature;
(2) adding 600g of first methanol into the reaction kettle cooled to room temperature in the step (1), leading out liquid in the reaction kettle after precipitation is carried out for 1h, and then adding 70g of third ethyl triacetate into the reaction kettle until the precipitate is dissolved;
(3) adding 600g of second methanol into the reaction kettle in the step (2), repeating the operation in the step (2) for 3 times to obtain a solid precipitate, and placing the solid precipitate in vacuum for drying to obtain 33g of resin B; GPC equipment measured the molecular weight Mw of the modified film-forming resin 9269 and the PDI 1.47.
Second, application example of the hydroxyl group-containing acid diffusion inhibitor
Example 2-1 and example 2-2
Examples 2-1 and 2-2 are examples of the use of the present invention to prepare two positive chemically amplified photoresists comprising hydroxy-acid diffusion inhibitor resins according to the following formulations:
acid diffusion inhibitor resin: example 2-1 resin A from example 1-1 was used; example 2-2 the resin B of example 1-2 was used;
acid-active film-forming resin: contains 2 acid-reactive groups and 2 polar groups in a ratio of 50: 50;
photosensitizer: triphenylsulfonium perfluorobutylsulfonate salt.
Organic solvent: PGMEA: cyclohexanone ═ 7: 3, a mixed organic solvent.
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 PGME. 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, and then drying the substrate to detect the photoetching result on an electron microscope, wherein the detection result is shown in attached figures 2 and 3.
The electron microscope tests show that the photoresist composition of the embodiment has good film forming property, and the photoresist film has no bad phenomena of brittle fracture, peeling and the like. The line edge roughness is less after the development, and the resolution ratio is high. Therefore, the hydroxyl-containing acid diffusion inhibitor resin provided by the embodiment of the invention is a high-molecular acid inhibitor, and can well control the photoacid diffusion of the 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. A hydroxyl-containing acid diffusion inhibitor characterized by the structural formula:
wherein R in the general formula (I)1、R2Is H or methyl; r3、R4One or more of alkyl with 1-40 hydrogen atoms and 1-20 carbon atoms, aryl or substituent containing sulfur/oxygen/nitrogen heteroatom; n is 5-200, naIs one or more of an alkyl group, an aryl group, or a functional structure containing a sulfur/oxygen/nitrogen heteroatom; n isbThe carbon chain contains one or more ether bonds and one or more ester bonds, and the number of carbon atoms is 1-20; wherein the moiety comprising said na and hydroxyl structure is a hydroxyl functional unit; comprising said R3、R4And nbThe moiety of (a) is a basic functional unit.
2. The hydroxyl group-containing acid diffusion inhibitor according to claim 1, characterized in that: the basic functional unit comprises any one of the following structures:
3. the hydroxyl group-containing acid diffusion inhibitor according to claim 1, characterized in that: the hydroxyl functional unit comprises any one of the following structures:
4. a process for preparing a hydroxyl group-containing acid diffusion inhibitor according to any one of claims 1 to 3, which comprises the steps of:
dissolving a monomer containing the hydroxyl functional unit and a monomer containing the alkaline functional unit in a first solvent to obtain a mixed solution containing an acid diffusion inhibitor monomer;
dissolving an initiator in a second solvent to obtain an initiator solution;
and mixing the initiator solution and the mixed solution, carrying out constant-temperature reflux polymerization at 40-90 ℃ for 2-30 hours, cooling to room temperature, carrying out separation treatment, and drying to obtain the hydroxyl-containing acid diffusion inhibitor.
5. The method of claim 4, wherein:
the mass percentage of the monomer containing the hydroxyl functional unit and the monomer containing the alkaline functional unit is (1-60): (40-99);
the dosage of the first solvent is 1-100 times of the total mass of the monomers;
the mass of the initiator is 0.3-15% of the total mass of the monomers in the mixed solution;
the dosage of the second solvent is 1 to 50 times of the mass of the initiator.
6. The production method according to claim 4 or 5, characterized in that: the initiator is one or at least two of azobisisobutyronitrile, azobisisoheptonitrile, tert-butyl peroxypivalate, tert-butyl hydroperoxide, benzoic acid hydroperoxide or benzoyl peroxide.
7. The production method according to claim 4 or 5, characterized in that: the first solvent and the second solvent are the same or different and are one or at least two of methanol, ethanol, dioxane, acetone, methyl ethyl ketone, tetrahydrofuran, methyl tetrahydrofuran, benzene, toluene, xylene, n-hexane, n-heptane, n-pentane, ethyl acetate, butyl acetate, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, petroleum ether, diethyl ether, n-butyl ether, chloroform, dichloroethane or trichloroethane.
8. A photoresist composition comprising the hydroxyl group-containing acid diffusion inhibitor according to any one of claims 1 to 3.
9. The photoresist composition of claim 8, wherein 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 hydroxyl-containing acid diffusion inhibitor; wherein the content of the acid diffusion inhibitor is 0.001-10%, the content of the film-forming resin with acid activity is 1-20%, the content of the photosensitizer is 0.01-10%, and the balance is organic solvent.
10. The photoresist composition according to claim 8 or 9, wherein the photoresist composition may further comprise 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.
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