CN104529795B - A compound for photoresist composition - Google Patents

Abstract

The present invention relates to a compound for a photoresist composition, which is suitable for excimer laser lithography, EUV lithography, EB lithography, and the like using ArF, KrF, and the like, and which exhibits excellent various photoresist capabilities such as sensitivity, resolution, and the like, and gives particularly improved line edge roughness and pattern profile.

Description

A compound for photoresist composition

technical field

The invention relates to a compound represented by formula (I), which is used for the photoresist composition for manufacturing computer chips and integrated circuits.

Background technique

Photoresist compositions are used in the microlithographic process of making miniaturized electronic components, such as in the manufacture of computer chips and integrated circuits. Typically, in these processes, a thin film coating of a photoresist composition is first applied to a substrate material, then the solvent in the photoresist composition is evaporated and the coating is fixed on the substrate, and finally the coated substrate is irradiated. The photoresist on the surface is exposed in an imaging mode.

Radiation causes the chemical transformation of the coated surface, with visible light, ultraviolet (UV) light, electron beam, and X-ray radiant energy being the types of radiation commonly used in microlithography today. After exposure, the coated substrate is treated with a developer solution to dissolve and remove the radiation-exposed or unexposed areas of the photoresist. The trend toward miniaturization of semiconductor components has led to the use of new photoresists that are sensitive at lower and lower wavelengths of radiation, and also to the use of complex multilevel systems to overcome the difficulties associated with this miniaturization.

In theory, the shorter the exposure wavelength, the higher the resolution. The wavelength of the exposure light source is gradually shortened to g-line with a wavelength of 436nm, i-line with a wavelength of 365nm, KrF excimer laser with a wavelength of 248nm, and ArF excimer laser with a wavelength of 193nm. The F ₂ excimer laser with a wavelength of 157nm is expected to be the next-generation exposure light source. As a next-generation exposure light source, EUV (Extreme Ultraviolet) having a wavelength of 13 nm or shorter has been proposed. The trend towards miniaturization of semiconductor devices has led to the use of new photoresists sensitive at lower and lower wavelengths of radiation, but also to the use of complex multilevel systems to overcome the difficulties posed by this miniaturization.

Photoresist resolution is defined as the smallest feature that a photoresist composition can transfer from a photomask to a substrate with high image edge sharpness after exposure and development. Photoresist resolutions on the order of sub-half a micron are required in many cutting-edge edge manufacturing applications today. As photoresist dimensions have been reduced below 150nm, the roughness of the photoresist pattern becomes a critical issue. Edge roughness, commonly referred to as line edge roughness, is generally observed as roughness along photoresist lines for line and space patterns, and as sidewall roughness for contact holes. Edge roughness can adversely affect the lithographic properties of the photoresist, especially in terms of reducing CD magnitude and transferring the line edge roughness of the photoresist to the substrate. Accordingly, photoresists that minimize edge roughness are highly desirable.

In general, high resolution extreme ultraviolet (UV) photoresists are available for patterning images with sub-quarter micron geometries. To date, there are three main EUV exposure techniques that offer significant advances in miniaturization, and these techniques use lasers emitting radiation at 248nm, 193nm and 157nm. Photoresists for extreme ultraviolet typically comprise a polymer with acid labile groups and deprotectable in the presence of acid, a photoactive component that generates an acid upon absorption of light, and a solvent.

A photoresist composition for semiconductor microfabrication using a photolithography process comprising: a resin having a structural unit derived from a compound having an acid-labile group, which is insoluble or hardly soluble in an aqueous alkali solution but passes Actions become soluble in aqueous base solutions; acid generators, which include compounds that generate acid by radiation; and basic compounds. U.S. Patent No. 5,914,219 discloses a photoresist composition comprising: a resin having a structural unit derived from a compound having an acid-labile group, which is insoluble or poorly soluble in an aqueous alkali solution but becomes soluble in an aqueous alkali solution; an acid generator comprising a compound that generates an acid by irradiation; and tetrabutylammonium hydroxide as a basic compound. In conventionally known photoresist compositions, there is a problem that line edge roughness occurs due to generation of sustained waves, ie, the smoothness of pattern side walls decreases, and as a result, the uniformity of line width deteriorates.

Contents of the invention

The technical problem to be solved by this invention is to provide a compound shown in formula (I), which shows excellent various photoresist capabilities such as sensitivity, clarity, etc. when used in photoresist compositions, and is particularly improved Line edge roughness and pattern profile.

According to one embodiment of the present invention, the present invention provides a kind of compound shown in the formula (I) that is used for photoresist composition:

Wherein R ₁ -R ₁₂ independently represent halogen, C ₁ -C ₂₀ straight or branched alkyl, C ₃ -C ₃₀ cyclic hydrocarbon group or C ₂ -C ₂₀ alkenyl, or two of R ₁ -R ₁₁ One or more are combined to form a nitrogen-containing heterocycle; Y is a counter anion.

In one embodiment of the present invention, R ₁ -R ₁₂ independently represent C ₁ -C ₆ linear or branched chain alkyl, and wherein at least one of R ₄ -R ₁₂ is fluorine.

In one embodiment of the present invention, R ₁ -R ₁₂ independently represent C ₁ -C ₈ straight or branched chain alkyl, and at least one of R ₄ -R ₁₂ is halogen or CF ₃ .

According to one embodiment of the present invention, examples of the halogen atom include fluorine atom, chlorine atom, bromine atom and iodine atom, preferably fluorine atom.

In one embodiment of the present invention, R ₁ -R ₁₂ independently represent butyl, methyl and octyl, and at least one of R ₄ -R ₁₂ is halogen or CF ₃ .

In one embodiment of the present invention, the compound represented by formula (I) is the compound of formula (A):

Wherein R ₁ -R ₃ are C ₁ -C ₈ alkyl groups, and Y is a counter anion.

In one embodiment of the present invention, R ₁ -R ₃ are C ₁ -C ₈ alkyl groups, and Y is a counter anion.

Compounds of formula (I) can be produced, for example, by reacting a tetraalkylammonium hydroxide, such as tetramethylammonium hydroxide, with the corresponding hydroxyalkylcarboxylic acid. The photoresist composition of the present invention may use two or more compounds represented by formula (I) in combination.

According to one embodiment of the present invention, the present invention provides a method for forming a pattern on a substrate surface, comprising:

(1) the step of applying a photoresist composition containing the compound of the present invention on a substrate,

(2) a step of forming a photoresist film by performing drying,

(3) the step of exposing said photoresist film to radiation,

(4) the step of baking the exposed photoresist film, and

(5) A step of developing the baked photoresist film with an alkaline developer to thereby form a photoresist pattern.

The photoresist composition containing the compound represented by formula (I) of the present invention comprises:

(1) one or more resins,

(2) The compound represented by formula (I), based on the total weight of the solid components of the photoresist composition, the content of the compound of formula (I) is usually 0.01-10% by weight, preferably 0.05-8% by weight, more Preferably 0.1-5% by weight;

(3) solvent;

The solid components refer to components in the photoresist composition except the solvent.

According to one embodiment of the present invention, the resin in the photoresist composition of the present invention can be:

1) Resins that can provide chemically amplified positive resists suitable for imaging at 248nm include: polymers containing vinylphenol and alkyl (meth)acrylate units, such as tert-butyl acrylate, tert-butyl methacrylate esters, methyladamantyl acrylate, methyladamantyl methacrylate, and other acyclic alkyl and alicyclic acrylates capable of photoacid-induced reactions, such as polymers in U.S. Patents 6,042,997 and 5,492,793, It is incorporated herein by reference.

2) Resins capable of providing chemically amplified positive resists suitable for imaging at wavelengths below 200 nm, such as 193 nm, include: i) polymers containing polymerized units of optionally substituted norbornene, as disclosed in U.S. Patent 5,843,624 Polymers; ii) Polymers containing alkyl (meth)acrylate units, such as tert-butyl acrylate, tert-butyl methacrylate, methyladamantyl acrylate, methyladamantyl methacrylate and other acyclic alkyl and cycloaliphatic (meth)acrylates; these polymers have been described in U.S. Patent 6,057,083.

According to one embodiment of the invention, the resin used in the photoresist for imaging below 200 nm, such as 193 nm, comprises units of the following general formulas (I), (II) and (III):

In the formula: R ₁ is a (C ₁ -C ₃ ) alkyl group; R ₂ is a (C ₁ -C ₃ ) alkylene group; L ₁ is a lactone group; n is 1 or 2.

Suitable monomers for forming the resins are commercially available and/or can be synthesized by known methods. The resins can be synthesized from the monomers readily by those skilled in the art using known methods as well as other commercially available starting materials. Mixtures of two or more resins may be used in the compositions of the present invention. The resin is present in the resist composition in sufficient amount to obtain a uniform coating of the desired thickness.

Typically, the resin is present in the composition in an amount of from 70 to 95 weight percent, based on the total weight of the solid components of the photoresist composition. Based on the total weight of the solid components of the photoresist composition, the photoresist composition of the present invention generally includes 80% by weight or more of the resin based on the sum of the solid components.

The resin is preferably insoluble or poorly soluble in an aqueous alkali solution and becomes soluble in an aqueous alkali solution by the action of an acid. The weight average molecular weight of the resin is preferably 500-100000, more preferably 1000-30000. The weight average molecular weight can be determined by gel permeation chromatography.

When the photoresist composition of the present invention contains a solvent, the ratio of resin to solvent (resin/solvent) is usually 1/1 to 1/1000, preferably 1/50 to 1/500.

According to one embodiment of the present invention, in the compound represented by formula (I), R ₁ -R ₁₂ independently represent C ₁ -C ₈ straight or branched chain alkyl, and wherein at least one of R ₄ -R ₁₂ is halogen or CF ₃ .

According to one embodiment of the present invention, in the compound represented by formula (I), R ₁ -R ₁₂ independently represent a C ₁ -C ₆ alkyl group, and at least one of R ₄ -R ₁₂ is fluorine.

According to one embodiment of the present invention, the C ₁ -C ₂₀ alkyl involved in the compound represented by formula (I) is preferably C ₁ -C ₁₅ straight chain alkyl and C ₃ -C ₁₅ branched chain alkyl, more preferably C ₁ -C ₁₀ straight-chain alkyl and C ₃ -C ₁₀ branched-chain alkyl, specific examples of which include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, Pentyl, isopentyl, tert-pentyl, neopentyl, 1,2-dimethylpropyl, 1-ethylpropyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl , dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, 1-methyl Ethyl, 1-methylpropyl, 2-methylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylbutyl, 2-ethylbutyl 1-methylpentyl, 2-methylpentyl, 3-methylpentyl and 4-methylpentyl.

According to one embodiment of the present invention, the C ₃ -C ₃₀ saturated cyclic hydrocarbon group involved in the compound represented by formula (I) preferably has 3-20 carbon atoms, more preferably 3-15 carbon atoms, especially preferably 3-8 Saturated cyclic hydrocarbon groups with 3 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, cycloheptyl and Cyclooctyl.

According to one embodiment of the present invention, the C ₂ -C ₂₀ alkenyl involved in the compound represented by formula (I) preferably has 2-5 carbon atoms, more preferably by combining the above-mentioned alkyl with vinyl (-CH =CH ₂ ).

The C ₁ -C ₂₀ alkyl group, C ₃ -C ₃₀ saturated cyclic hydrocarbon group and C ₂ -C ₂₀ alkenyl group may have one or more substituents. Examples of substituents include halogen atoms, haloalkyl such as C ₁ -C ₂₀ haloalkyl, alkyl such as C ₁ -C ₂₀ alkyl, alkoxy, hydroxyalkoxy, alkoxyalkoxy, alkoxycarbonyl Oxy, alkoxycarbonylalkoxy, alkoxycarbonyl, aryl, heteroaryl and aralkyl. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, preferably a fluorine atom. As the haloalkyl group, a fluoroalkyl group is preferred. Examples of the alkyl group include the same ones as described above. Examples of aryl groups include phenyl, biphenyl, fluorenyl, naphthyl, anthracenyl and phenanthrenyl. Examples of the heteroaryl group include the above-mentioned aryl groups in which one or more carbon atoms constituting the aromatic ring are replaced with heteroatoms such as oxygen atoms, sulfur atoms and nitrogen atoms. Examples of the aralkyl group include benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl and 2-naphthylethyl. As the aralkyl group, a C ₁ -C ₄ alkyl group substituted by an aryl group is preferred, a C ₁ -C ₂ alkyl group substituted by an aryl group is more preferred, and a methyl group substituted by an aryl group is especially preferred. The aryl, heteroaryl and aralkyl groups may have one or more substituents such as C ₁ -C ₁₀ alkyl, haloalkyl (such as C ₁ -C ₈ haloalkyl, preferably C ₁ -C ₄ haloalkyl ), alkoxy, hydroxyl and halogen atoms.

According to one embodiment of the present invention, the photoresist composition of the present invention further includes a solvent. The amount of the solvent is generally 90% by weight or more, preferably 92% by weight or more, more preferably 94% by weight or more of the total amount of the photoresist composition of the present invention. A photoresist composition containing a solvent may preferably be used to produce a thin layer photoresist pattern.

The solvent that can be used for the photoresist composition of the present invention can be a conventional solvent in the field of photoresist, including for example: ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, isophor Ketones, methylisoamylone, 2-heptanone 4-hydroxyl, and 4-methyl-2-pentanone; C ₁ to C ₁₀ aliphatic alcohols such as methanol, ethanol, and propanol; alcohols containing aromatic groups , such as benzyl alcohol; cyclic carbonates, such as ethylene carbonate and propylene carbonate; aliphatic or aromatic hydrocarbons (such as hexane, toluene, xylene, etc.); cyclic ethers, such as di ethylene glycol; propylene glycol; hexanediol; ethylene glycol monoalkyl ethers, such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether; ethylene glycol alkyl ether acetates, such as methyl solvent Cellosolve acetate and ethyl cellosolve acetate; glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol methyl ether, diethylene glycol monoalkyl Ethers, such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diglyme; propylene glycol monoalkyl ethers, such as propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, and propylene glycol butyl ether; propylene glycol alkyl ethers Ether acetates, such as propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, and propylene glycol butyl ether acetate; propylene glycol alkyl ether propionates, such as propylene glycol methyl ether propionate, Propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, and propylene glycol butyl ether propionate; 2-methoxyethyl ether (diglyme); solvents with both ether and hydroxyl moieties, such as formazan Oxybutanol, ethoxybutanol, methoxypropanol, and ethoxypropanol; esters such as methyl acetate, ethyl acetate, propyl acetate, and butyl acetate methylpyruvate, pyruvate Ethyl ester; ethyl 2-hydroxypropionate, methyl 2-hydroxy 2-methylpropionate, ethyl 2-hydroxy 2-methylpropionate, methyl glycolate, ethyl glycolate, buty Glycolic Acid, Methyl Lactate, Ethyl Lactate, Propyl Lactate, Butyl Lactate, Methyl 3-Hydroxypropionate, Ethyl 3-Hydroxypropionate, Propyl 3-Hydroxypropionate, 3-Hydroxypropionate Butylate, Methyl 2-Hydroxy 3-Methylbutyrate, Methyl Methoxy Acetate, Ethyl Methoxy Acetate, Propyl Methoxy Acetate, Butyl Methoxy Acetate, Methyl Ethoxy Acetate, Ethyl Ethoxy Acetate, Propyl Ethoxy Acetate, Butyl Ethoxy Acetate, Methyl Propoxy Acetate, Ethyl Propoxy Acetate, Propyl Propoxy Acetate, Butyl Propoxy Acetate, Methyl Butoxy Acetate, Ethyl Butoxy Acetate, Propyl Butoxy Acetate, Butyl Butoxy Acetate Butoxy acetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, 2- Methyl ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, 2- Butoxy ethyl propionate, 2-butoxy propyl propionate, 2-butoxy butyl propionate, 3-methoxy methyl propionate, 3-methoxy ethyl propionate, 3- Propyl methoxypropionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, 3- Butyl ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, butyl 3-propoxypropionate, 3- Methyl butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, and butyl 3-butoxypropionate; oxyisobutyrate, e.g., methyl -2-Hydroxyisobutyrate, methyl α-methoxyisobutyrate, ethyl methoxyisobutyrate, methyl α-ethoxyisobutyrate, ethyl α-ethoxyisobutyrate , methyl β-methoxyisobutyrate, β-methoxyisobutyric acid Ethyl ester, methyl beta-ethoxyisobutyrate, ethyl beta-ethoxyisobutyrate, methyl beta-isopropoxyisobutyrate, ethyl beta-isopropoxyisobutyrate, beta - Isopropyl isopropoxy isobutyrate, β-isopropoxy butyl isobutyrate, β-butoxy methyl isobutyrate, β-butoxy ethyl isobutyrate, β-butoxy butyl isobutyrate, methyl alpha-hydroxyisobutyrate, ethyl alpha-hydroxyisobutyrate, isopropyl alpha-hydroxyisobutyrate, and butyl alpha-hydroxyisobutyrate; have ether and hydroxyl moieties Both solvents, such as methoxybutanol, ethoxybutanol, methoxypropanol, and ethoxypropanol; and other solvents, such as dibasic esters, and gamma-butyrolactone; ketone ether derivatized substances, such as diacetone alcohol methyl ether; ketone alcohol derivatives, such as acetol or diacetone alcohol; amide derivatives, such as dimethylacetamide or dimethylformamide, anisole, and mixtures thereof.

According to one embodiment of the present invention, the photoresist composition, the composition of the solvent in the photoresist composition is preferably: (1) 15 parts by weight of ethylene glycol dimethyl ether, (2) 40 parts by weight of ethyl acetate and (3) 5 parts by weight of γ-butyrolactone.

According to one embodiment of the present invention, the photoresist composition of the present invention also includes various other additives, such as colorants, non-actinically active dyes, anti-striation agents, plasticizers, tackifiers, dissolution inhibitors, etc. agents, coating aids, sensitivity enhancers, and other photoacid generators.

The photoresist composition of the present invention may also contain surfactants (such as fluorinated surfactants) to improve film thickness uniformity, and sensitizers that can transmit energy from a specific range of wavelengths to various exposure wavelengths.

The photoresist composition of the present invention may contain one or more basic compounds to prevent the formation of T-tops (t-tops) or bridges on the imaging surface of the photoresist, the content of the basic compound usually accounting for 0.01-1% by weight of solid components. The basic compound is preferably a basic nitrogen-containing organic compound, and examples thereof include amine compounds such as aliphatic amines and aromatic amines and ammonium salts. Examples of aliphatic amines include primary, secondary and tertiary amines.

According to one embodiment of the present invention, the photoresist composition contains a basic compound selected from the group consisting of pyridine, amine, ammonium hydroxide, trioctylamine, diethanolamine and tetrabutylammonium hydroxide. Based on the total weight, the content of the basic compound is generally 0.01 to 1% by weight of the solid component.

By applying radiation such as light, electron beams, etc. to the resin itself or to the photoresist composition of the present invention, the resin will decompose to generate acid. In the photoresist composition of the present invention, the resin functions not only as a resin component but also as an acid generator.

Although the resin functions as an acid generator in the photoresist composition of the present invention as described above, the photoresist composition of the present invention may further contain other acid generators. The acid generator may be selected from various compounds that generate acid by irradiating the acid generator itself or a photoresist composition containing the acid generator with rays. Examples of the acid generator include salts, haloalkyltriazine compounds, disulfone compounds, diazomethane compounds having a sulfonyl group, sulfonate ester compounds, and imide compounds having a sulfonyloxy group.

Examples of the salt include salts in which one or more nitro groups are contained in an anion, and salts in which one or more ester groups are contained in an anion. Examples of salts include diphenyliodotriflate, (4-methoxyphenyl)phenyliodide hexafluoroantimonate, (4-methoxyphenyl)phenyliodide triflate Salt, bis(4-tert-butylphenyl)iodotetrafluoroborate, bis(4-tert-butylphenyl)iodohexafluorophosphate, bis(4-tert-butylphenyl)iodohexafluoroantimonate Salt, bis(4-tert-butylphenyl) iodotrifluoromethanesulfonate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium (1-adamantylmethyl Oxy)carbonyl difluoromethanesulfonate, triphenylsulfonium(3-hydroxymethyl-1-adamantyl)methoxycarbonyl difluoromethanesulfonate, triphenylmadium 1-(hexahydro-2 -Oxo-3,5-methylene-2H-cyclopent[b]furan-6-yloxycarbonyl) difluoromethanesulfonate, triphenylsulfonium (4-oxo-1-adamantyloxy ) carbonyl difluoromethanesulfonate, triphenylsulfonium (3-hydroxy-1-adamantyl) methoxycarbonyl difluoromethanesulfonate, (4-methylphenyl) diphenylsulfonium nonafluorobutane Sulfonate, (4-methoxyphenyl)diphenylsulfonium hexafluoroantimonate, (4-methoxyphenyl)diphenylsulfonium trifluoromethanesulfonate, (4-methylphenyl ) diphenylsulfonium trifluoromethanesulfonate, (4-methylphenyl) diphenylsulfonium heptadecafluorooctanesulfonate, (2,4,6-trimethylphenyl) diphenylsulfonium three Fluoromethanesulfonate, (4-tert-butylphenyl)diphenylsulfonium trifluoromethanesulfonate, (4-phenylphenylthio)diphenylsulfonium hexafluorophosphate, (4-phenylbenzene Thio)diphenylsulfonium hexafluoroantimonate, 1-(2-naphthoylmethyl)tetrahydrothiophene hexafluoroantimonate, 1-(2-naphthoylmethyl)tetrahydrothiophene trifluoromethanesulfonic acid salt, (4-hydroxy-1-naphthyl)dimethylsulfonium hexafluoroantimonate and (4-hydroxy-1-naphthyl)dimethylsulfonium trifluoromethanesulfonate.

Examples of haloalkyltriazine compounds include 2-methyl-4,6-bis(trichloromethyl)-1,3,5-triazine, 2,4,6-tris(trichloromethyl)-1, 3,5-triazine, 2-phenyl-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-chlorophenyl)-4,6-bis(tri Chloromethyl)-1,3,5-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-( 4-methoxy-1-naphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(benzo[d][1,3]dioxa Cyclopenten-5-yl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxystyryl)-4,6-bis(tri Chloromethyl)-1,3,5-triazine, 2-(3,4,5-trimethoxystyryl)-4,6-bis(trichloromethyl)-1.3,5-triazine, 2-(3,4-dimethoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(2,4-methoxystyryl )-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(2-methoxystyryl)-4,6-bis(trichloromethyl)-1, 3,5-triazine, 2-(4-butoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine and 2-(4-pentyloxybenzene vinyl)-4,6-bis(trichloromethyl)-1,3,5-triazine.

Examples of sulfonate compounds include 1-benzoyl-1-phenylmethyl p-toluenesulfonate (commonly known as "benzoin tosylate"), 2-benzoyl-2-p-toluenesulfonate Hydroxy-2-phenylethyl ester (commonly known as "alpha-hydroxymethylbenzoin tosylate"), 1,2,3-benzene-tris(methanesulfonate), p-toluenesulfonic acid 2,6-Dinitrobenzyl ester, 2-nitrobenzyl p-toluenesulfonate and 4-nitrobenzyl p-toluenesulfonate.

Examples of disulfone compounds include diphenyldisulfone and bis(p-tolyl)disulfone.

Examples of diazomethane compounds having a sulfonyl group include bis(phenylsulfonyl)diazomethane, bis(4-chlorophenylsulfonyl)diazomethane, bis(p-tolylsulfonyl)diazomethane, bis( 4-tert-butylphenylsulfonyl)diazomethane, bis(2,4-xylylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane and (benzoyl)(phenylsulfonyl Acyl)diazomethane.

Examples of imide compounds having a sulfonyloxy group include N-(phenylsulfonyloxy)succinimide, N-(trifluoromethylsulfonyloxy)succinimide, N-(trifluoromethylsulfonyloxy)succinimide, Methylsulfonyloxy)phthalimide, N-(trifluoromethylsulfonyloxy)-5-norbornene-2,3-dicarboximide, N-(trifluoromethyl Sulfonyloxy)naphthalimide and N-(10-camphorsulfonyloxy)naphthalimide. Two or more acid generators may be used in combination.

An acid generator can generate an acid when irradiated with activating radiation, such as EUV radiation, electron beam radiation, radiation at a wavelength of 193 nanometers, or other radiation source. The acid generator is present in the photoresist composition in an amount sufficient to produce a latent image in a coating of the composition upon exposure to activating radiation. For example, based on the total solid weight of the photoresist composition, the content of the acid generator may suitably be 1-20% by weight.

The photoresist composition of the present invention can be used as a chemically amplified photoresist composition.

The photoresist pattern can be produced in the following steps: (1) a step of applying a photoresist composition on a substrate, (2) a step of forming a photoresist film by performing drying, (3) making the photoresist film a step of exposing to radiation, (4) a step of baking the exposed photoresist film, and (5) developing the baked photoresist film with an alkaline developer to thereby form a photoresist pattern step.

Application of the photoresist composition to the substrate is generally performed using conventional equipment such as a spin coater. The prepared photoresist composition solution can be applied to the substrate by any conventional method used in the photoresist art, including dipping, spraying, and spin coating. Prior to application, the photoresist composition is preferably filtered through a filter with a pore size of 0.2 μm. When spin coating, for example, the percent solids content of the photoresist solution can be adjusted to provide the desired coating thickness, taking into account the type of spinning device used and the time allowed for the spinning process. Suitable substrates include silicon, aluminum, polymer resins, silicon dioxide, doped silicon dioxide, silicon nitride, tantalum, copper, polysilicon, ceramics, aluminum/copper hybrids; gallium arsenide and others such III/V compound. Photoresist can also be applied over the anti-reflective coating.

Photoresist coatings prepared by the described process are particularly suitable for application to silicon/silicon dioxide wafers, for example for the fabrication of microprocessors and other small integrated circuit components. Aluminum/alumina wafers can also be used. The substrate may also comprise various polymeric resins, especially transparent polymers such as polyester.

The formation of the photoresist film is usually carried out with a heating device such as a hot plate or a pressure reducer, the heating temperature is usually 50-200° C., and the working pressure is usually 1-1.0×10 5 Pa.

The obtained photoresist film is exposed to radiation using an exposure system. Exposure is typically done through a mask having a pattern corresponding to the desired photoresist pattern. Examples of the exposure source include light sources that radiate UV-region laser light (such as KrF excimer laser (wavelength: 248 nm), ArF excimer laser (wavelength: 193 nm), and F2 laser (wavelength: 157 nm)) and light sources from solid-state laser light sources (such as YAG or semiconductor laser) laser wavelength conversion to radiate a source of harmonic laser in the far UV region or vacuum UV region.

The baking temperature of the exposed photoresist film is usually 50-200°C, preferably 70-150°C.

Development of the baked photoresist film is usually performed using a developing device. The alkaline developer used can be any one of various aqueous alkaline solutions used in the art. Generally, an aqueous solution of tetramethylammonium hydroxide or (2-hydroxyethyl)trimethylammonium hydroxide (commonly known as "choline") is often used. After development, the formed photoresist pattern is preferably washed with ultrapure water, and remaining water on the photoresist pattern and the substrate is preferably removed.

The photoresist composition of the present invention provides a photoresist pattern with good resolution, therefore, the photoresist composition of the present invention is suitable for ArF excimer laser lithography, KrF excimer laser lithography, EUV (extreme ultraviolet) Photolithography, EUV immersion lithography and EB (Electron Beam) lithography, the photoresist composition of the present invention is especially suitable for EUV (Extreme Ultraviolet) lithography and EB (Electron Beam) lithography.

Example

The present invention will be described more specifically through examples below, and these examples should not be construed as limiting the scope of the present invention. "%" and "parts" used to indicate the content of any component and the amounts of any substance used in the following examples and comparative examples are by weight unless otherwise specified. The weight average molecular weights of any substances used in the following examples are values measured by gel permeation chromatography using standard polystyrene as a standard reference material. The structures of the compounds were confirmed by NMR and mass spectrometry.

Synthetic example

Synthesis Example 1

Equimolar 10-cyclopropyl-4-(trifluoromethyl)anthracene-1-carboxylic acid was mixed with appropriate amount of ethyl acetate and 37% aqueous tetrabutylammonium hydroxide solution, and the resulting mixture was stirred at room temperature for 1 hour. An appropriate amount of methanol was added to the resulting mixture, and the resulting mixture was stirred at room temperature for 16 hours. The resulting solution was concentrated to obtain compound D1 in 67% yield.

1H-NMR (500.16MHz, d6-dimethylsulfoxide) δppm: 0.96(t, 12H), 1.33(t, 6H), 1.50-1.52(m, 8H), 3.35(m, 6H), 6.70(d, 1H), 7.32(m, 2H), 7.29-7.32(m, 1H), 7.67-7.82(m, 4H)

13C-NMR (125.77MHz, d6-dimethylsulfoxide) δppm: 9.33, 12.55, 13.80, 20.81, 28.01, 60.17, 112.92, 122.8, 123.11, 123.66, 127.12, 128.29, 131.6, 135.2, 136.74

Synthesis Example 2

A mixture of equimolar 10-cyclopropyl-4-(trifluoromethyl)anthracene-1-carboxylic acid and an appropriate amount of methanol was mixed with 37% tetramethylammonium hydroxide methanol solution, and the resulting mixture was stirred at room temperature for 16 Hour. The resulting mixture was concentrated, and the resulting residue was mixed with an appropriate amount of ethyl acetate. The resulting solution was washed three times with ion-exchanged water. The resulting solution was concentrated to obtain compound D2 in 63% yield.

1H-NMR (500.16MHz, d6-dimethylsulfoxide) δppm: 0.40-0.65(m, 4H), 1.50(t, 1H), 2.85(m, 9H), 6.53(d, 1H), 6.86(d, 1H), 7.32(t, 2H), 7.50-7.67(m, 3H)

13C-NMR (125.77MHz, d6-dimethylsulfoxide) δppm: 9.3, 12.5, 51.1, 112.9, 121.6, 122.8, 123.1, 126.3, 127.3, 127.7, 128.3, 131.6, 135.2, 136.7, 156.7

Synthesis Example 3

A mixture of equimolar tetraoctylammonium bromide and an appropriate amount of methanol was mixed with 10-cyclopropyl-4-(trifluoromethyl)anthracene-1-carboxylic acid, and the resulting mixture was stirred at room temperature for 16 hours. The resulting mixture was concentrated, and the resulting residue was mixed with an appropriate amount of ethyl acetate. The resulting solution was washed with an appropriate amount of 5% aqueous sodium bicarbonate solution, and then washed twice with ion-exchanged water. The resulting solution was concentrated to obtain compound D3 in 47% yield.

1H-NMR (500.16MHz, d6-dimethylsulfoxide) δppm: 0.96(t, 6H), 1.29(t, 12H), 1.33(t, 4H), 1.50-1.52(m, 7H), 3.35(m, 4H), 6.70(d, 1H), 7.32(m, 2H), 7.67-7.73(m, 2H)

13C-NMR (125.77MHz, d6-dimethylsulfoxide) δppm: 9.3, 12.5, 14.1, 22.8, 25.8, 27.7, 29.1, 31.9, 60.4, 112.9, 121.6, 122.8,, 123.1, 126.3, 127.3, 127.7, 128.3 , 131.6, 135.2, 136.7, 156.7

Photoresist preparation example

Preparation Example 1

A photoresist composition was prepared by mixing the compound of formula (I), resin, and acid generator in a solvent according to the following ratio, and filtering through a fluororesin filter with a pore size of 0.2 μm.

components Content (wt%) Compound of formula (I) 0.2 resin 4.2 acid generator 0.6 solvent 95

The formula (I) compound in the preparation example 1 uses the compound A1 prepared in the synthesis example 1; Resin uses ECPMA The acid generator uses 2,6-dinitrobenzyl p-toluenesulfonate; the solvent uses ethylene glycol dimethyl ether.

Preparation Example 2

A photoresist composition was prepared by mixing the compound of formula (I), resin, and acid generator in a solvent according to the following ratio, and filtering through a fluororesin filter with a pore size of 0.2 μm.

components Content (wt%) Compound of formula (I) 0.2 resin 4.2 acid generator 0.6 solvent 95

The formula (I) compound in the preparation example 2 uses the compound A2 prepared in the synthesis example 2; Resin uses ECPMA The acid generator uses 2,6-dinitrobenzyl p-toluenesulfonate; the solvent uses ethylene glycol dimethyl ether.

Preparation Example 3

A photoresist composition was prepared by mixing the compound of formula (I), resin, and acid generator in a solvent according to the following ratio, and filtering through a fluororesin filter with a pore size of 0.2 μm.

components Content (wt%) Compound of formula (I) 0.2 resin 4.2 acid generator 0.6 solvent 95

The formula (I) compound in the preparation example 3 uses the compound A3 prepared in the synthesis example 3; Resin uses ECPMA The acid generator uses 2,6-dinitrobenzyl p-toluenesulfonate; the solvent uses ethylene glycol dimethyl ether.

Preparation Example 4

A photoresist composition was prepared by mixing the compound of formula (I), resin, acid generator and basic compound in a solvent in the following proportions, and filtering through a fluororesin filter with a pore size of 0.2 μm.

components Content (wt%) Compound of formula (I) 0.2 resin 4.15 acid generator 0.6 basic compound 0.05 solvent 95

The formula (I) compound in the preparation example 4 uses the compound A1 prepared in the synthesis example 1; Resin uses ECPMA The acid generator uses 2,6-dinitrobenzyl p-toluenesulfonate; the basic compound uses pyridine; the solvent uses ethylene glycol dimethyl ether.

Preparation Example 5

A photoresist composition was prepared by mixing the compound of formula (I), resin, acid generator and basic compound in a solvent in the following proportions, and filtering through a fluororesin filter with a pore size of 0.2 μm.

components Content (wt%) Compound of formula (I) 0.2 resin 4.15 acid generator 0.6 basic compound 0.05 solvent 95

The formula (I) compound in the preparation example 5 uses the compound A2 prepared in the synthesis example 2; Resin uses ECPMA The acid generator uses 2,6-dinitrobenzyl p-toluenesulfonate; the basic compound uses pyridine; the solvent uses ethylene glycol dimethyl ether.

Preparation Example 6

A photoresist composition was prepared by mixing the compound of formula (I), resin, acid generator and basic compound in a solvent in the following proportions, and filtering through a fluororesin filter with a pore size of 0.2 μm.

components Content (wt%) Compound of formula (I) 0.2 resin 4.15 acid generator 0.6 basic compound 0.05 solvent 95

The formula (I) compound in the preparation example 6 uses the compound A3 prepared in the synthesis example 3; Resin uses ECPMA The acid generator uses 2,6-dinitrobenzyl p-toluenesulfonate; the basic compound uses pyridine; the solvent uses ethylene glycol dimethyl ether.

Preparation Example 7

A photoresist composition was prepared by mixing the compound of formula (I), resin, and acid generator in a solvent according to the following ratio, and filtering through a fluororesin filter with a pore size of 0.2 μm.

components Content (wt%) Compound of formula (I) 0.2 resin 4.2 acid generator 0.6 Solvent E1 95

The formula (I) compound in the preparation example 7 uses the compound A3 prepared in the synthesis example 3; Resin uses ECPMA The acid generator uses 2,6-dinitrobenzyl p-toluenesulfonate.

Preparation Example 8

A photoresist composition was prepared by mixing the compound of formula (I), resin, acid generator and basic compound in a solvent in the following proportions, and filtering through a fluororesin filter with a pore size of 0.2 μm.

components Content (wt%) Compound of formula (I) 0.2 resin 4.15 acid generator 0.6 basic compound 0.05 Solvent E1 95

The formula (I) compound in the preparation example 8 uses the compound A3 prepared in the synthesis example 3; Resin uses ECPMA The acid generator uses 2,6-dinitrobenzyl p-toluenesulfonate; the basic compound uses pyridine.

Preparation Example 9

A photoresist composition was prepared by mixing the compound of formula (I), resin, acid generator and basic compound in a solvent in the following proportions, and filtering through a fluororesin filter with a pore size of 0.2 μm.

components Content (wt%) Compound of formula (I) 0.2 resin 4.15 acid generator 0.6 basic compound 0.05 Solvent E1 95

The formula (I) compound in the preparation example 9 uses the compound A2 prepared in the synthesis example 2; Resin uses ECPMA The acid generator uses 2,6-dinitrobenzyl p-toluenesulfonate; the basic compound uses pyridine.

Preparation Example 10 (Comparative Example 1)

Compound B, resin, and acid generator were mixed in a solvent in the following proportions, and filtered through a fluororesin filter with a pore size of 0.2 μm to prepare a photoresist composition.

components Content (wt%) Compound B 0.2 resin 4.2 acid generator 0.6 solvent 95

Resin using ECPMA The acid generator uses 2,6-dinitrobenzyl p-toluenesulfonate; the solvent uses ethylene glycol dimethyl ether.

Preparation example 11 (comparative example 2)

Compound B, resin, acid generator, and basic compound were mixed in a solvent in the following proportions, and filtered through a fluororesin filter with a pore size of 0.2 μm to prepare a photoresist composition.

components Content (wt%) Compound B 0.2 resin 4.15 acid generator 0.6 basic compound 0.05 solvent 95

Resin using ECPMA The acid generator uses 2,6-dinitrobenzyl p-toluenesulfonate; the basic compound uses pyridine; the solvent uses ethylene glycol dimethyl ether.

Preparation example 12 (comparative example 3)

Compound B, resin, acid generator, and basic compound were mixed in a solvent in the following proportions, and filtered through a fluororesin filter with a pore size of 0.2 μm to prepare a photoresist composition.

components Content (wt%) Compound B 3 resin 15 acid generator 1 basic compound 1 Solvent E1 80

Resin using ECPMA The acid generator uses 2,6-dinitrobenzyl p-toluenesulfonate; the basic compound uses pyridine; the solvent uses ethylene glycol dimethyl ether.

In the aforementioned preparation examples, the solvent E1 used contained the following components: (1) 15 parts by weight of ethylene glycol dimethyl ether, (2) 40 parts by weight of ethyl acetate and (3) 5 parts by weight of gamma-butyrolactone . Compound B used in the comparative examples is a compound having the following structure:

In the foregoing examples, compounds A1-A3 have the same anions as compound B.

Photolithography

The photolithography process is carried out by conventional methods in this field. Each silicon wafer was exposed to hexamethyldisilazane at 110° C. for 60 seconds on a direct hot plate, and each photoresist composition prepared above was spin-coated on the silicon wafer to a film thickness of 0.10 μm after drying. After applying each photoresist composition, the silicon wafer thus coated with each photoresist composition was prebaked at a temperature of 110° C. for 60 seconds. Using extreme ultraviolet (EUV) exposure of a commercially available writing electron beam lithography system, each silicon wafer on which each photoresist film had been formed was exposed to a line and space pattern while gradually changing the exposure amount.

After exposure, each silicon wafer was subjected to a post-exposure bake for 60 seconds at a temperature of 100-110° C. on a hot plate, and then developed with 2.5 wt % (2-hydroxyethyl)trimethylammonium hydroxide in water for 60 seconds .

The developed resist patterns on the silicon substrates were observed with a scanning electron microscope after development, and the results are shown in the table below.

The smoothness of the surface of the pattern wall: observe the surface of the pattern wall of the dense line pattern with a scanning electron microscope. When the line edge is rough, it is judged as "×" (poor), and when it is not observed, it is judged as "○" (good) ).

Resolution: Set the exposure amount of each photoresist pattern into a 1:1 line and space pattern as the effective sensitivity. Determines the minimum linewidth of a line and space pattern exposed and developed at an effective sensitivity.

Resolution and smoothness of patterned wall surfaces

The results in the above table show that the photoresist composition containing the compound of the present invention can produce relatively good smoothness, resolution and effective sensitivity of the pattern wall surface, and the photoresist composition of the present invention provides a high-efficiency photoresist pattern and is especially suitable for KrF excimer laser lithography, EUV lithography and EB lithography.

The foregoing description of the invention illustrates and describes the invention. In addition, the present disclosure only describes the preferred embodiments of the present invention, and it should be understood that the present invention can be changed or improved within the scope of the inventive concept expressed herein, and such changes or improvements are consistent with the above teachings and/or technologies in the related field. Or knowledge is commensurate. Accordingly, the description is not intended to limit the invention to the form disclosed herein. Furthermore, it is intended that the appended claims be construed to cover alternative embodiments.

Claims (2)

1. compound shown in the formula for photoetching compositions (A):

Wherein R ₁-R ₃for C ₁-C ₈alkyl, Y is counter anion.

2. compound according to claim 1, is characterized in that R ₁-R ₃represent butyl, methyl and octyl group independently.