KR20110131904A - Photoacid generator, mathod for manufacturing the same and resist composition comprising the same - Google Patents

Abstract

PURPOSE: A photoacid generator has the slow diffusion velocity of acid generated in the photo exposure time, short diffusion distance, moderate acidity, and is provided to improve line width roughness. CONSTITUTION: A photoacid generator is in the chemical formula 1. In the chemical formula 1, Y is selected from the group consisting of C3-30 cycloalkyl group and C3-30 cycloalkenyl group. Q1 and Q2 is halogen atom respectively. X is selected from the group consisting of alkanediyl, alkanediyl, NR', S, O CO or the combination thereof. R is selected from the group consisting of hydrogen and alkyl group. n is integer of 0-5. A+ is an organic counter ion.

Description

Photoacid generator, a manufacturing method thereof and a resist composition comprising the same {PHOTOACID GENERATOR, MATHOD FOR MANUFACTURING THE SAME AND RESIST COMPOSITION COMPRISING THE SAME}

The present invention relates to a photoacid generator, a method for manufacturing the same, and a resist composition including the same, wherein the acid diffusion at the time of exposure is slow, the diffusion distance is short, and an appropriate acidity can be exhibited to improve LWR characteristics. The present invention relates to a photoacid generator capable of controlling elution in a solvent such as pure water, a method for preparing the same, and a resist composition including the same.

As the generation of the microfabrication method using photolithography changes, more high-resolution pororesist is required. For this purpose, chemically amplified resists have been developed, and such chemically amplified resist compositions contain photoacid generators.

In the chemically amplified resist composition, the photoacid generator is a factor that allows the chemically amplified resist to have excellent physical properties in terms of resolution, line width roughness (LWR), sensitivity, etc. together with the resist composition. Many kinds of photoacid generators have been researched to prepare them.

In particular, in order to improve the diffusion rate and transparency of acid, which is one of physical properties such as excellent resolution, LWR, sensitivity, etc., a compound used as a photoacid generator has undergone many changes and experiments on its cation portion. However, studies to improve the properties of chemically amplified resists by changing the anion portion of the photoacid generator are insufficient.

The invention of the anion portion of the photoacid generator is newly made based on the experimental result that the anion side may have more influence than the cation side as a physical and chemical property which substantially improves the fluidity of the acid and the properties of the composition of the resist. In addition, there is a growing demand for a photoacid generator that can control permeability while reducing acid diffusion rate.

In addition, in recent years, as a light source of chemically amplified resists, it is shorter in the g-ray or i-ray region, which is conventionally used, so that it is far ultraviolet, KrF excimer laser, ArF excimer laser, EUV (extreme ultraviolet), X-ray Research on lithography using electron beams is ongoing. In particular, since the exposure process is performed using pure water in the immersion ArF process, the photoresist composition used in the immersion ArF process does not dissolve the photoacid generator or acid generated therefrom into the pure water. Not required is characteristic.

An object of the present invention is a mine which is capable of improving the LWR characteristics by exhibiting an appropriate acidity at a slow diffusion rate, a short diffusion distance and improving the LWR characteristics, and controlling elution in solvents such as pure water used in the process. It is to provide a generator.

It is another object of the present invention to provide a resist composition including the photoacid generator and a method of manufacturing the same.

In order to achieve the above object, a photoacid generator according to an embodiment of the present invention is represented by the following formula (1).

[Formula 1]

In Formula 1, Y is any one selected from the group consisting of a cycloalkyl group having 3 to 30 carbon atoms and a cycloalkenyl group having 3 to 30 carbon atoms, wherein Q ₁ and Q ₂ are each independently a halogen atom, and X is Alkanediyl, alkenediyl, NR ', S, O, CO and any one selected from the group consisting of a combination thereof, R' is any one selected from the group consisting of hydrogen and alkyl groups, n is 0 to An integer of 5, wherein A + is an organic counterion.

According to another aspect of the present invention, a method for preparing a photoacid generator is a first step of dissolving a compound represented by Formula 8 in a solvent and reacting with a reducing agent to obtain a compound represented by Formula 6, represented by Formula 7 below. The second step of obtaining a compound represented by the following formula (4) by reacting the compound represented by the formula (6) under a basic catalyst, and the substitution of the compound represented by the formula (4) and the compound represented by the formula (5) It includes a third step of obtaining a compound represented by the formula (1).

[Formula 8]

[Formula 6]

[Formula 7]

[Formula 4]

[Formula 5]

[Formula 1]

In Formula 1, Formula 4, Formula 5, Formula 6, Formula 7 and Formula 8, R ₆ is an alkyl group, Q ₁ , Q ₂ and Q ₅ are each independently a halogen atom, and Y is 3 to Any one selected from the group consisting of a cycloalkyl group of 30 and a cycloalkenyl group of 3 to 30 carbon atoms, wherein X is selected from the group consisting of alkanediyl, alkenediyl, NR ', S, O, CO and combinations thereof Any one, wherein R 'is any one selected from the group consisting of hydrogen and alkyl groups, n is an integer of 0 to 5, and A + is an organic covalent ion. M + is any one selected from the group consisting of Li +, Na + and K +, and Z- is (OSO ₂ CF ₃ )-, (OSO ₂ C ₄ F ₉ )-, (OSO ₂ C ₈ F ₁₇ )-, ( N (CF ₃ ) ₂ )-, (N (C ₂ F ₅ ) ₂ )-, (N (C ₄ F ₉ ) ₂ ), (C (CF ₃ ) ₃ )-, (C (C ₂ F ₅ ) ₃ )-, (C (C ₄ F ₉ ) ₃ )-, F-, Cl-, Br-, I-, BF _4- , AsF ₆ -and PF _6- .

Photoresist according to another embodiment of the present invention provides a chemically amplified resist composition comprising a photoacid generator.

Hereinafter, the present invention will be described in more detail.

Definitions of terms used in the present specification are as follows.

Unless otherwise specified herein, a halogen atom means any one selected from the group consisting of fluorine, chlorine, bromine and iodine.

Unless stated otherwise in the specification, an alkyl group includes a primary alkyl group, a secondary alkyl group, and a tertiary alkyl group.

Unless stated otherwise in the specification, alkanediyl is a divalent atomic group minus two hydrogen atoms in alkanes, and may be represented by the general formula —C _n H _2n — and alkenediyl ) Is a divalent atom group minus two hydrogen atoms in alkene, and may be represented by the general formula -C _n H _n- .

Unless otherwise specified in the present specification, a perfluoroalkyl group means an alkyl group in which some hydrogen atoms or all hydrogen atoms are substituted with fluorine, and a perfluoroalkoxy group means an alkoxy group in which some hydrogen atoms or all hydrogen atoms are substituted with fluorine. do.

Unless stated otherwise in the specification, all compounds or substituents may be substituted or unsubstituted. Herein, the substituted Iran hydrogen is a halogen atom, a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an amino group, a thio group, a methylthio group, an alkoxy group, a nitrile group, an aldehyde group, an epoxy group, an ether group, an ester group, a carbonyl group, Substituted with any one selected from the group consisting of acetal groups, ketone groups, alkyl groups, perfluoroalkyl groups, cycloalkyl groups, heterocycloalkyl groups, allyl groups, benzyl groups, aryl groups, heteroaryl groups, derivatives thereof, and combinations thereof Means that.

Unless stated otherwise in the present specification, the prefix hetero means that one to three heteroatoms selected from the group consisting of N, O, S and P are substituted with a carbon atom.

Unless otherwise specified in the present specification, an alkyl group is a linear or crushed alkyl group having 1 to 10 carbon atoms, alkanediyl is alkanediyl having 1 to 10 carbon atoms, alkenediyl alkenediyl having 2 to 10 carbon atoms, and allyl group has 2 to 10 carbon atoms. 10 allyl groups, alkoxy groups are alkoxy groups having 1 to 10 carbon atoms, perfluoroalkyl groups are perfluoroalkyl groups having 1 to 10 carbon atoms, perfluoroalkoxy groups are perfluoroalkoxy groups having 1 to 10 carbon atoms, and hydroxyalkyl groups A hydroxyalkyl group having 1 to 10 carbon atoms, a cycloalkyl group is a cycloalkyl group having 3 to 32 carbon atoms, a heterocycloalkyl group is a heterocycloalkyl group having 2 to 32 carbon atoms, an aryl group having 6 to 30 carbon atoms, and a heteroaryl group having 2 to 30 carbon atoms It means a heteroaryl group.

In the present specification, Me stands for methyl group.

Photoacid generators which are one embodiment of the present invention are represented by the following formula (1).

[Formula 1]

In Formula 1, Q ₁ and Q ₂ are each independently a halogen atom, preferably a fluoro atom, n is an integer of 0 to 5, preferably an integer of 0 to 2.

In Formula 1, X is any one selected from the group consisting of alkanediyl, alkenediyl, NR ', S, O, CO, and combinations thereof, and R' is any selected from the group consisting of hydrogen and alkyl groups. One.

Wherein X is _{-O-, -OCH 2 -, -OCH (} Cl) -, -CO-, -COCH 2 -, -COCH 2 CH 2 -, -CH 2 -, -CH 2 CH 2 -, -CH 2 -O-, -CH ₂ -O-CH _2- , -CH ₂ CH ₂ -O-, -CH ₂ -O-CH ₂ CH _2- , -CH ₂ CH ₂ -O-CH _2- , -CH ₂ CH ₂ CH ₂ -O-, -CH ₂ -O-CH ₂ CH ₂ CH _2- , -CH ₂ CH ₂ -O-CH ₂ CH _2- , -CH ₂ CH ₂ CH ₂ -O-CH _2- , -CH (CH ₃ )-, -C (CH ₃ ) ₂ CH _2- , -CH (CH ₃ ) CH ₂ , -CH (CH ₂ CH ₃ )-, -CH (OCH ₃ )-, -C (CF ₃ ) (OCH ₃ )-, -CH ₂ -S-, -CH ₂ -S-CH _2- , -CH ₂ CH ₂ -S-, -CH ₂ -S-CH ₂ CH _2- , -CH ₂ CH ₂ -S-CH _2- , -CH ₂ CH ₂ CH ₂ -S-, -CH ₂ -S-CH ₂ CH ₂ CH _2- , -CH ₂ CH ₂ -S-CH ₂ CH _2- , -CH ₂ CH ₂ CH ₂ -S-CH _2- , -CH (CH ₂ ) CH-, -C (CH ₂ CH ₂ )-, -CH ₂ CO-, -CH ₂ CH ₂ CO-, -CH (CH ₃ ) CH ₂ CO-, -CH (OH)-, -C (OH) (CH ₃ )-, -CH (F)-, -CH (Br)-, -CH (Br) CH (Br)-, -CH = CH-, -CH ₂ CH = CH-, -CH = CHCH _2- , -CH = CH-O-, -CH = CH-S- and -CH = CHCO- can be any one selected from the group have.

In Formula 1, Y is any one selected from the group consisting of a cycloalkyl group having 3 to 30 carbon atoms and a cycloalkenyl group having 3 to 30 carbon atoms.

The Y is an adamantyl group, a norbornyl group, a polycyclic cycloalkyl group containing a nobonyl group having 10 to 30 carbon atoms, a monocyclic cycloalkyl having 3 to 14 carbon atoms, a bicyclic cycloalkyl having 4 to 20 carbon atoms, and a tricyclic having 10 to 30 carbon atoms. It may be any one selected from the group consisting of a formula cycloalkyl group and a tetracyclic cycloalkyl group having 10 to 30 carbon atoms.

In the hydrogen of Y, 1 to 5 said hydrogens are alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, perfluoroalkyl groups having 1 to 4 carbon atoms, perfluoroalkoxy groups having 1 to 4 carbon atoms, and 1 carbon atoms. And substituted with any one selected from the group consisting of hydroxyalkyl group, halogen atom, hydroxy group, cyano group, nitro group, amino group, thio group, methylthio group, methoxy group, OR ', COR' and COOR ' Can be. R 'is any one selected from the group consisting of an alkyl group and an aryl group.

In addition, the Y may be any one selected from the group consisting of the following formulas (1-a to 1-i).

[Formula 1-a] [Formula 1-b] [Formula 1-c]

[Formula 1-d] [Formula 1-e] [Formula 1-f]

[Formula 1-g] [Formula 1-h] [Formula 1-i]

In Formulas 1-a to 1-i, R ₁₁ and R ₁₂ are each independently hydrogen, an alkyl group, an alkoxy group, a perfluoroalkyl group, a perfluoroalkoxy group, a halogen atom, a hydroxyl group, a carboxyl group, a cyano group It may be substituted with any one selected from the group consisting of, nitro group, amino group, thio group, methylthio group, methoxy group, OR ', COR' and COOR '. R 'is any one selected from the group consisting of an alkyl group and an aryl group.

A, c and d are each independently an integer of 0 to 9, b is an integer of 0 to 11, e is an integer of 0 to 15, f is an integer of 0 to 7, 0≤c + d ≦ 17 and 0 ≦ c + f ≦ 15.

Preferably, in Formulas 1-a, 1-b, 1-d, and 1-g, R ₁₁ represents hydrogen, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a perfluorine having 1 to 4 carbon atoms. Group consisting of a roalkyl group, a perfluoroalkoxy group having 1 to 4 carbon atoms, a hydroxyalkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxy group, a cyano group, a nitro group, an amino group, a thio group, a methylthio group and a methoxy group It may be any one selected from.

In addition, in Chemical Formulas 1-c, 1-e, 1-f, 1-h, and 1-i, R ₁₁ and R ₁₂ are each independently hydrogen, an alkyl group having 1 to 6 carbon atoms, and an alkoxy having 1 to 6 carbon atoms. Groups, perfluoroalkyl groups of 1 to 4 carbon atoms, perfluoroalkoxy groups of 1 to 4 carbon atoms, hydroxyalkyl groups of 1 to 6 carbon atoms, halogen atoms, hydroxy groups, cyano groups, nitro groups, amino groups, thio groups, It may be any one selected from the group consisting of methylthio group, methoxy group and combinations thereof.

Preferably, the moiety represented by the following Formula 3, which is an anion part of the compound represented by Formula 1, may be any one selected from the group consisting of the following Formulas 1-i to 1-xx.

[Formula 3]

[Formula 1-i to 1-xx]

The photoacid generator may introduce an alicyclic ring to the compound represented by Formula 3, which is an anion part of the compound represented by Formula 1, to control acid diffusion rate, and may be highly permeable when a light source such as ArF is used. Photoacid generators exhibiting characteristics can be provided.

In Formula 1, A + is an organic counterion.

Specifically, the moiety represented by the following Formula 2, which is a cation moiety of the compound represented by Formula 1, may be any one selected from the group consisting of the following Formulas 2a and 2b.

(2)

[Formula 2a]

[Formula 2b]

In Formulas 2a and 2b, R ₁ and R ₂ are each independently selected from the group consisting of hydrogen, an alkyl group, an allyl group, a perfluoroalkyl group, an aryl group, and a combination thereof, and R ₁ and R ₂ May combine with each other to form a saturated or unsaturated hydrocarbon ring having 3 to 30 carbon atoms.

R ₄ is any one selected from the group consisting of a halogen atom, an alkyl group, an alkoxy group, an aryl group, a thioalkoxy group, an alkoxycarbonylmethoxy group, a thiophenoxy group, and a combination thereof.

R ₃ and R ₅ are each independently selected from hydrogen, an alkyl group, an allyl group, a perfluoroalkyl group, an aryl group, and a combination thereof.

In Chemical Formulas 2a and 2b, examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, phenyl group, hexyl group and octyl group, and the alkoxy group may include methoxy group and ethoxy group. , Propoxy group, butoxy group, hexyloxy group, octyloxy group and the like.

In addition, the moiety represented by Chemical Formula 2, which is a cationic moiety of the compound represented by Chemical Formula 1, may be any one selected from the group consisting of Chemical Formulas 2-i to 2-xx.

[Formula 2-i to 2-xx]

The moiety represented by the following Chemical Formula 2, which is a cation moiety of the compound represented by Chemical Formula 1, may be any one selected from the group consisting of Chemical Formulas 3a and 3b.

[Formula 3a]

[Formula 3b]

In Formulas 3a and 3b, R ₁ is any one selected from the group consisting of hydrogen, an alkyl group, an allyl group, a perfluoroalkyl group, an aryl group, and a combination thereof.

R ₂ and R ₃ are each independently selected from hydrogen, an alkyl group, an allyl group, a perfluoroalkyl group, an aryl group, and a combination thereof.

R ₄ is any one selected from the group consisting of a halogen atom, an alkyl group, an alkoxy group, an aryl group, a thioalkoxy group, an alkoxycarbonylmethoxy group, a thiophenoxy group, and a combination thereof.

In Formulas 3a and 3b, examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, phenyl group, hexyl group and octyl group, and the alkoxy group may be a methoxy group or an ethoxy group. , Propoxy group, butoxy group, hexyloxy group, octyloxy group and the like.

In addition, the moiety represented by Chemical Formula 2, which is a cationic moiety of the compound represented by Chemical Formula 1, may be any one selected from the group consisting of Chemical Formulas 3-i to 3-ix.

[Formula 3-i to 3-ix]

According to another embodiment of the present invention, a method for preparing a photoacid generator represented by Chemical Formula 1 may include dissolving a compound represented by Chemical Formula 8 in a solvent and reacting with a reducing agent to obtain a compound represented by Chemical Formula 6 below. A second step of obtaining a compound represented by the following formula (4) by reacting the compound represented by the formula (7) and the compound represented by the formula (6) under a basic catalyst, and the compound represented by the formula (4) and the compound represented by the formula (5) And a third step of obtaining a compound represented by Chemical Formula 1 by performing a substitution reaction.

The first step includes obtaining a compound represented by the following Chemical Formula 6 by dissolving the compound represented by the following Chemical Formula 8 in a solvent and adding a reducing agent.

[Formula 8]

[Formula 6]

In Formula 6 and Formula 8, R ₆ is an alkyl group, and specifically, any one selected from the group consisting of methyl group, trifluoromethyl group, trichloromethyl group, tribromomethyl group, triiodemethyl group, ethyl group, propyl group and butyl group Can be. Q ₁ and Q ₂ are each independently a halogen atom, and preferably a fluoro atom. M + is any one selected from the group consisting of Li +, Na + and K +.

As the solvent for dissolving the compound represented by Formula 8 in the first step reaction, any solvent can be used as long as it can dissolve the ester compound represented by Formula 8.

As the solvent, any one selected from the group consisting of esters, ethers, lactones, ketones, amides, alcohols, and combinations thereof may be used, and preferably alcohol solvents, dichloromethane, chloroform, dichloroethane. It may be used together with any one selected from the group consisting of acetonitrile, toluene, dimenylformamide, tetrahydrofuran, dimethylformamide, dimenylsulfoxide and combinations thereof, but the present invention is not limited thereto.

The alcohol solvent is methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, t-butyl alcohol, oxo butyl alcohol, undecyl alcohol, hydroxydecyl alcohol, heptyl alcohol , 2-methyl-1-pentyl alcohol, allyl alcohol, ethoxylcarbonylmethyl alcohol, methoxyethyl alcohol, 1-methoxy-2propyl alcohol, benzyl alcohol, phenethyl alcohol, cyclohexyl alcohol, menthyl alcohol, tetrahydro It may be any one selected from the group consisting of loperfuryl alcohol, tetrahydropyranyl alcohol, cyanobutyl alcohol, 4-hydroxy-2-butanone, and combinations thereof, but the present invention is not limited thereto.

As the reducing agent, any one selected from the group consisting of NaBH ₄ , LiAlH ₄ , BH ₃ -THF, NaBH ₄ -AlCl ₃ , NaBH ₄ -LiCl, LiAl (OMe) _3, and combinations thereof may be used.

The compound represented by Formula 8 and the reducing agent may be used in a molar ratio of 1: 1 to 1: 5, preferably in a molar ratio of 1: 2 to 1: 3.5. When using the compound represented by the formula (8) and the reducing agent in the molar ratio, it is possible to increase the yield of the product compared to the use of the reducing agent.

Specifically, the first step of the reaction may include preparing a reaction mixture by dissolving the compound represented by Chemical Formula 8 in the solvent in an ice bath and dropwise adding a reducing agent, and removing the ice bath from the reaction mixture and heating the mixture. Can be.

The stirring may be preferably performed at 20 to 120 ° C. for 2 to 6 hours, and more preferably at 60 to 100 ° C. for 3 to 5 hours. In the case of the stirring process in the temperature and time range, the yield of the product can be increased and the formation of side products can be minimized.

The reaction of the reaction mixture is terminated (quenched), the solvent is removed and the reaction product is obtained.

The method for obtaining the reactant can be generally used as long as it removes the solvent from the reaction mixture and obtains the reactant. For example, by recrystallization, a solvent that dissolves the obtained compound and a solvent that does not dissolve well are mixed. The method of solidifying using, the method of extracting by concentration using a solvent, or the method of concentrating can be used.

Preferably, the method for obtaining the reactants, the solvent is removed from the reaction mixture, dissolved in distilled water again, the solution is acidified to pH 5 to 6, the reaction mixture is concentrated, and alcohol is added again to form a slurry The method of removing phosphorus inorganic salt and crystallizing the filtrate using diethyl ether etc. can be used.

The compound represented by Formula 8 reacts an alkoxide with a halide to prepare a dialkoxy halogen compound having two alkoxy groups, and then oxidizes one of two alkoxy compounds of the dialkoxy halogen compound. Intermediate production step of preparing a compound represented by 9 and the compound represented by the formula (9) can be prepared through the sulfonation step of preparing a compound represented by the formula (8) by reacting with the inorganic sulfite.

[Formula 9]

In Formula 9, R ₆ is an alkyl group, and specifically may be any one selected from the group consisting of methyl group, trifluoromethyl group, trichloromethyl group, tribromomethyl group, triiodemethyl group, ethyl group, propyl group and butyl group. . Q ₁ to Q ₃ are each independently a halogen atom, and preferably a fluoro atom.

Specifically, in the intermediate generation step, the alkoxide may be an alkoxy alkene having 3 to 10 carbon atoms including a double bond of carbon and carbon, and specifically, may be methoxy ethene or ethoxy ethene. The halide may be an alkyl halide, and specifically, may be perfluoromethane, dibromodifluoromethane, perbromomethane or perchloromethane.

In the intermediate production step, the alkoxide and the halide may be reacted in an alcohol solvent, and sodium hyposulfite (Na ₂ S ₂ O ₄ , sodium hydrosulfite) and sodium hydrogen carbonate (NaHCO ₃ ) may be added and reacted together. In addition, the reaction of oxidizing one of the two alkoxy of the produced dialkoxy halogen compound may be carried out in the presence of an oxidizing agent, specifically KHSO ₅ may be used as the oxidizing agent.

As the inorganic sulfite used in the sulfonation step, sodium hyposulfite may be specifically used, and sodium hydrogen carbonate (NaHCO ₃ ) may be added to react together. When the sulfonation reaction is performed using the sodium hyposulfite, the compound represented by Chemical Formula 8 may be prepared by oxidizing the organic sulfonate. In this case, as the oxidizing agent, hydrogen peroxide (H ₂ O ₂ ) or sodium tungstate (sodium tungstate, Na ₂ WO ₄ ) may be used.

The second step includes a process of obtaining a compound represented by Chemical Formula 4 by reacting the compound represented by Chemical Formula 7 with the compound represented by Chemical Formula 6 under a basic catalyst.

[Formula 7]

[Formula 4]

In the above formulas (4) and (7), each of Q ₁ , Q ₂ and Q ₅ is independently selected from halogen atoms, and is preferably a fluoro atom. N is an integer of 0 to 5, preferably an integer of 0 to 2.

M + is any one selected from the group consisting of Li +, Na + and K +.

Since X and Y are the same as those described in the description of the compound represented by Formula 1, the description thereof is omitted.

The basic catalyst may be any one selected from the group consisting of triethylamine, dienylamine, pyridine, dienylisopropyl amine, and combinations thereof. When the basic catalyst is used in the second step reaction, a desired product can be obtained with a minimum reaction time, thereby increasing the yield of the reaction.

The reaction of the second step may be carried out under a solvent, the solvent may be any one selected from the group consisting of esters, ethers, lactones, ketones, amides, alcohols, and combinations thereof. The solvent may be any one selected from the group consisting of dichloromethane, chloroform, dichloroethane, acetonitrile, toluene, methyl acetate, ethyl acetate, and combinations thereof.

The compound represented by Chemical Formula 6 and the compound represented by Chemical Formula 7 may be reacted in a molar ratio of 1: 1 to 1: 3, preferably in a molar ratio of 1: 1.1 to 1: 1.5. When the compounds represented by Formula 6 and Formula 7 are reacted at the molar ratio, both compounds may be exhausted, thereby increasing the efficiency of the reaction.

In addition, the compound represented by the formula (6) and the basic catalyst can be reacted in a molar ratio of 1: 1 to 1: 4, preferably can be reacted in a molar ratio of 1: 1.1 to 1: 2. When the compound represented by Chemical Formula 6 is reacted with the basic catalyst at the molar ratio, it may be easier to promote the reaction time and remove the residual basic catalyst.

The second step reaction may specifically include dissolving the compound represented by Chemical Formula 6 and the basic catalyst in a solvent, and stirring the compound represented by Chemical Formula 7 dissolved in a solvent while heating and stirring.

The stirring may be preferably performed at a temperature of 40 to 120 ° C. for 0.5 to 6 hours, and more preferably at a temperature of 60 to 90 ° C. for 2 to 3 hours. In the case of the stirring process in the temperature and time range, the yield of the product can be increased and the formation of side products can be minimized.

The reaction of the reaction mixture is terminated (quenched), the solvent is removed and the reactant is crystallized to obtain a compound represented by the formula (4).

The method for the crystallization may be used without limitation, if the method of removing the solvent from the reaction mixture and crystallize the reactant, preferably, after washing the reaction mixture to separate the organic layer to remove the solvent and separated by column chromatography The reaction may be obtained by vacuum drying.

The third step includes a process of obtaining a compound represented by Chemical Formula 1 by performing a substitution reaction between the compound represented by Chemical Formula 4 and the compound represented by Chemical Formula 5.

[Formula 5]

In Chemical Formula 5, Z- is (OSO ₂ CF ₃ )-, (OSO ₂ C ₄ F ₉ )-, (OSO ₂ C ₈ F ₁₇ )-, (N (CF ₃ ) ₂ )-, (N ( C ₂ F ₅ ) ₂ )-, (N (C ₄ F ₉ ) ₂ ), (C (CF ₃ ) ₃ )-, (C (C ₂ F ₅ ) ₃ )-, (C (C ₄ F ₉ ) ₃ )-, F-, Cl-, Br-, I-, BF _4- , AsF ₆ -and PF ₆ -and any one selected from the group, wherein A + is an organic opion, a detailed description of the formula Since it is the same as that described in the description about the compound represented by 1, the description is abbreviate | omitted.

The compound represented by the formula (4) and the compound represented by the formula (5) is in a molar ratio of 1: 1 to 5: 1, preferably in a molar ratio of 1: 1 to 3: 1, more preferably 1: 1 to 2: 1 Can be used as the molar ratio of. When used in the molar ratio it is possible to minimize the reaction treatment time and to suppress side reactions due to the use of excessive reactants.

The substitution reaction may be a method of solidifying and recovering by using a recrystallization method or a mixture of a solvent (good solvent) that dissolves well with a solvent (poor solvent) that does not dissolve well. The method can also be used.

Preferably, it can be dissolved in dichloromethane and water to form two layers, followed by stirring to cause a substitution reaction, which is advantageous in that no additional method for product separation is necessary when using this two-layer reaction method. Do. The stirring may be performed for 2 to 6 hours, or may be performed for 2 to 4 hours. When the reaction is performed in the above time range, there is an effect that the yield of the product can be increased as much as possible.

When the compound represented by Chemical Formula 1 is prepared through the above process, the compound represented by Chemical Formula 1 may be prepared in an efficient and simple manner.

Another embodiment of the resist composition of the present invention includes a photoacid generator represented by the formula (1). Since the said resist composition is based on the structure of a normal resist composition, the description is abbreviate | omitted.

The photoacid generator according to the present invention can improve the LWR (line width roughness) characteristics by showing a low acid diffusion rate at the time of exposure, a short diffusion distance and proper acidity, and a solvent such as pure water used in the process. Elution can be controlled. In addition, the method for producing a photoacid generator according to the present invention can produce the photoacid generator in an efficient and simple manner.

Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily practice the present invention. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.

Synthesis of Photoacid Generator

Synthesis Example 1 of Photoacid Generator

Synthesis of Adamantyl-3,3-difluoro-3-sulfo-propyl ether diphenyl methyphenyl sulfonium salt

First step) 1,1-difluoro-3-methoxy-3-oxopropane-1-sulfonate sodium salt (sodium 1,1-difluoro-3-methoxy-3) under an ice bath as shown in Scheme 1 below. Dissolve 83 g (0.376 mol) of -oxopropane-1-sulfonate in 160 ml of methanol (methanol, MeOH) and 1.2 L of THF (tetrahydrofuran), and slowly add dropwise 44 g (1.16 mol) of sodium borohydride (NaBH ₄ ). The reaction mixture was prepared. After completion of the dropwise addition, the reaction mixture was removed by heating the ice bath and stirred at about 60 ° C. for about 4 hours.

The reaction mixture was quenched with distilled water and then the solvent was removed. The mixed reaction product which was crucified again with distilled water was dissolved and acidified to pH of 5 to 6 with concentrated hydrochloric acid.

The acidified mixed reaction product was concentrated, and methanol was added again to filter the slurry to remove inorganic salts. The filtrate from which the slurry was removed was washed twice with hexane, the methanol layer was concentrated again and then crystallized using diethyl ether.

The white solid obtained by crystallization was dried in vacuo and its structure was confirmed by ¹ H NMR. 68.5 g (0.346 mol) yield 95% of 1,1-difluoro-3-hydroxypropane-1-sulfonate sodium salt (sodium 1,1-difluoro-3-hydroxypropane-1-sulfonate) were obtained.

¹ H-NMR (D 2 O): (ppm) 2.38 (t, 2H) 4.18 (t, 2H)

[Scheme 1]

For reference, the 1,1-difluoro-3-methoxy-3-oxopropane-1-sulfonate sodium salt may be prepared through a reaction as in Scheme 2 below.

[Scheme 2]

Second Step) As shown in Scheme 3, the 1,1-difluoro-3-hydroxypropane-1-sulfonate sodium salt prepared in the first step (sodium 1,1-difluoro-3-hydroxypropane-1 20 g (0.101 mol) of -sulfonate and ₂₃ ml (0.165 mol) of triethylamine (Et ₃ N) were dissolved in 400 ml of ethyl acetate, and the solution was stirred at 80 ° C. 20 g (0.1172 mol) of adamantyl chloride dissolved in 200 ml of ethyl acetate was added dropwise to the solution, followed by heating and stirring for 2.5 hours.

After the reaction of the reaction mixture was terminated, washed three times with 200 ml of 1N hydrochloric acid solution, once with 200 ml of 10% sodium carbonate solution, and the organic layer of the reaction mixture was separated to remove the solvent.

The reaction product was separated by column chromatography using silica gel and dried in vacuo to confirm the structure by ¹ H NMR. 3-adamantan-1-yloxy-1,1-difluoro-propane-1-sulfonic acid salt represented by A of Scheme 3 below (3- (Adamantan-1-yloxy) -1,1-difluoro 30g (yield 80%) of -propane-1-sulfonic acid salt) was obtained.

¹ H-NMR (dimethylsulfoxide- d ₆ , tetramethylsilane): (ppm) 1.67-1.98 (m, 15H), 2.45 (t, 2H), 4.52 (t, 2H)

Scheme 3

Third Step) As in Scheme 4 below, 3-adamantane-1-yloxy-1,1-difluoro-propane-1-sulfonate salt (3- (Adamantan-1-1) prepared in the second step was prepared. -yloxy) -1,1-difluoro-propane-1-sulfonic acid salt) 8.5 g (0.0255 mol) and diphenyl methylphenyl sulfonium trifluoro methane sulfonate salt represented by B in Scheme 4 below. 10 g (0.0234 mol) of methane sulfonium salt) was dissolved in 100 ml of dichloromethane (methylene chloride, MC) and 100 ml of water, and the mixture was stirred vigorously for 3 hours so that the reaction occurred in a reaction mixture formed of two layers.

After stirring the reaction mixture, the organic layer was taken and the progress of the reaction was confirmed by ¹⁹ F NMR. After completion of the reaction, the organic layer was collected and the slurry from which the solvent was removed was washed with dichloromethane as a good solvent and hexane as a poor solvent to obtain a solid, and the solid was dried under reduced pressure. The compound represented by B was obtained. The obtained solid was adamantyl-3,3-difluoro-3-sulfo-propyl-ether diphenyl methylphenyl sulfonium salt represented by C in Scheme 4 below (Adamantyl-3,3-difluoro-3-sulfo 13.3 g (yield 94.3%) of -propyl ether diphenyl methylphenyl sulfonium salt) was obtained, and the structure thereof was confirmed by ¹ H NMR.

¹ H-NMR (chloroform- d ₃ , tetramethylsilane): (ppm) 1.67-1.98 (m, 15H), 2.45 (t, 2H), 2.47 (s, 3H), 4.76 (t, 2H), 7.48 ( d, 2H), 7.65-7.76 (m, 12H)

[Scheme 4]

Synthesis of Resin

Synthesis Example 1 of Resin

3-bicyclo [2.2.1] hept-5-en-2-yl-3-hydroxy propionic acid t-butyl ester (3-Bicyclo [2.2.1] hept-5-en-2-yl-3 -hydroxy-propionic acid t-butyl ester), 1-methyl adamantane acrylate (1-methyl adamantane acrylate, 2-methyl-2-adamantyl acrylate), gamma-butyrolactone methyl acrylate (gamma-butyrolactone acrylate, 2-oxotetrahydrofuran-3-yl acrylate) was charged at a molar ratio of 1: 1: 1 (33 parts: 33 parts: 33 parts), and as a polymerization solvent, 1,4-dioxane was added three times the total mass of the reaction monomer. Used. As an initiator, azobisisobutyronitrile was used at a rate of 4 mol% based on the total molar amount of the monomers, and reacted at 65 ° C. for 16 hours.

After the reaction, the reaction solution was precipitated using n-hexane, and dried in vacuo to obtain a resin represented by the following formula (11). The precipitated copolymer was one having a weight average molecular weight of 8,500.

[Formula 11]

Preparation of resist

Comparative Example 1

4 parts by weight of triphenyl sulfonium triflate as a photoacid generator (PAG) and tetramethylammonium hydroxide as basic additive (BASE) based on 100 parts by weight of the resin represented by Formula 11 obtained in Synthesis Example 1 of the resin. Parts by weight were dissolved in 1,000 parts by weight of propylene glycol methyl ether acetate and then filtered through a 0.2 um membrane filter to prepare a resist solution.

The resist solution was applied to a substrate using a spinner, and dried at 110 ° C. for 90 seconds to form a 0.20 um thick film. The formed film was exposed to light using an ArF excimer laser stepper (lens numerical aperture: 0.78) and heat-treated at 110 ° C. for 90 seconds. The formed film was developed with a 2.38 wt% tetramethylammonium hydroxide aqueous solution for 40 seconds, and then washed and dried to form a resist pattern.

Example 1

Except that 3 parts by weight of adamantyl-3,3-difluoro-3-sulfo-propyl-ether diphenyl methylphenyl sulfonium salt represented by C in Scheme 4 as a photoacid generator was used. In the same manner as in Comparative Example 1, a resist solution was prepared and physical properties thereof were evaluated.

[Example 2]

Except that 5 parts by weight of adamantyl-3,3-difluoro-3-sulfo-propyl-ether diphenyl methylphenyl sulfonium salt represented by C in Scheme 4 as a photoacid generator was used. In the same manner as in Comparative Example 1, a resist solution was prepared and physical properties thereof were evaluated.

Example 3

Except that 7 parts by weight of adamantyl-3,3-difluoro-3-sulfo-propyl-ether diphenyl methylphenyl sulfonium salt represented by C in Scheme 4 as a photoacid generator was used. In the same manner as in Comparative Example 1, a resist solution was prepared and physical properties thereof were evaluated.

The physical properties of Comparative Example 1 and Examples 1 to 3 were shown in Table 1 by evaluating sensitivity, resolution, and line width roughness (LWR).

In the case of LWR, the roughness of the pattern was observed for the 0.10 um line-and-space (L / S) pattern formed after development. When the pattern obtained in Comparative Example 1 was 1, the degree of improvement in terms of LWR was 1-5. The numbers were expressed as, and the larger the number, the better the LWR characteristics.

In the case of sensitivity, the exposure amount for forming a 0.10 um line-and-space (L / S) pattern formed after development with a line width of 1 to 1 was used as the optimum exposure amount, and the minimum pattern size resolved when the optimum exposure amount was used as the sensitivity was used as the resolution. It was shown.

Suzy
(100 parts by weight) PAG ¹⁾
(Parts by weight) BASE ²⁾
(Parts by weight) Sensitivity
(mJ / cm ² ) resolution
(nm) LWR Example 1 Synthesis Example 1 of Resin 3 0.5 17 70 4 Example 2 Synthesis Example 1 of Resin 5 0.5 16 80 3 Example 3 Synthesis Example 1 of Resin 7 0.5 13 70 3 Comparative Example 1 Synthesis Example 1 of Resin 3 0.5 15 90 2

1) Photoacid generator (PAG)

Examples 1 to 3: adamantyl-3,3-difluoro-3-sulfo-propyl-ether diphenyl methylphenyl sulfonium salt represented by C in Scheme 4 prepared in Synthesis Example 1 of the photoacid generator

Comparative Example 1: Triphenyl Sulfonium Triflate

2) Basic Additive (BASE): Tetramethylammonium Hydroxide

The photoacid generator (PAG) used in Examples 1 to 3 was prepared by introducing an alicyclic ring to the anion of the photoacid generator, which is similar to that of a trilate or a non-plate photoacid generator. While maintaining the acidity, the acid diffusion rate was slow and the diffusion distance was short.

Referring to the physical property measurement results of Table 1, it showed much better performance than the conventional triplerate type in terms of LWR and resolution. The introduction of aromatics into the anion of the photoacid generator showed excellent results in terms of transparency when irradiated with light, and once the acid was generated from the photoacid generator and moved to the anion form, the aromatic ring had no effect on the transparency. According to the size of, there is a favorable effect that can control the diffusion rate and diffusion distance of the acid showed a distinctive feature from the conventional photoacid generator.

Although the preferred embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements of those skilled in the art using the basic concepts of the present invention defined in the following claims are also provided. It belongs to the scope of rights.

Claims (8)

A photoacid generator represented by the following formula (1).
[Chemical Formula 1]

(In Formula 1,
Y is any one selected from the group consisting of a cycloalkyl group having 3 to 30 carbon atoms and a cycloalkenyl group having 3 to 30 carbon atoms,
Q ₁ and Q ₂ are each independently a halogen atom,
X is any one selected from the group consisting of alkanediyl, alkenediyl, NR ', S, O, CO and combinations thereof, wherein R' is any one selected from the group consisting of hydrogen and alkyl groups,
N is an integer of 0 to 5,
A + is an organic counterion) The method of claim 1,
The Y is an adamantyl group, a norbornyl group, a polycyclic cycloalkyl group containing a nobonyl group having 10 to 30 carbon atoms, a monocyclic cycloalkyl having 3 to 14 carbon atoms, a bicyclic cycloalkyl having 4 to 20 carbon atoms, and a tricyclic having 10 to 30 carbon atoms. The photoacid generator is any one selected from the group consisting of a formula cycloalkyl group and a tetracyclic cycloalkyl group having 10 to 30 carbon atoms. The method of claim 1,
Wherein Y is any one selected from the group consisting of the formula 1a to 1-i.
[Formula 1-a] [Formula 1-b] [Formula 1-c]

[Formula 1-d] [Formula 1-e] [Formula 1-f]

[Formula 1-g] [Formula 1-h] [Formula 1-i]

(In Chemical Formulas 1-a to 1-i,
R ₁₁ and R ₁₂ are each independently an alkyl group, an alkoxy group, a perfluoroalkyl group, a perfluoroalkoxy group, a halogen atom, a hydroxy group, a carboxyl group, a cyano group, a nitro group, an amino group, a thio group, a methylthio group, It may be substituted with any one selected from the group consisting of a methoxy group, OR ', COR' and COOR ', wherein R' is any one selected from the group consisting of an alkyl group and an aryl group,
A, c and d are each independently an integer of 0 to 9, b is an integer of 0 to 11, e is an integer of 0 to 15, f is an integer of 0 to 7, 0≤c + d ≦ 17 and 0 ≦ c + f ≦ 15) The method of claim 1,
In the general formula (1) wherein X is _{-O-, -OCH 2 -, -OCH (} Cl) -, -CO-, -COCH 2 -, -COCH 2 CH 2 -, -CH 2 -, -CH 2 CH 2 - , -CH ₂ -O-, -CH ₂ -O-CH _2- , -CH ₂ CH ₂ -O-, -CH ₂ -O-CH ₂ CH _2- , -CH ₂ CH ₂ -O-CH _2- , -CH ₂ CH ₂ CH ₂ -O-, -CH ₂ -O-CH ₂ CH ₂ CH _2- , -CH ₂ CH ₂ -O-CH ₂ CH _2- , -CH ₂ CH ₂ CH ₂ -O- CH _2- , -CH (CH ₃ )-, -C (CH ₃ ) ₂ CH _2- , -CH (CH ₃ ) CH _2- , -CH (CH ₂ CH ₃ )-, -CH (OCH ₃ )- , -C (CF ₃ ) (OCH ₃ )-, -CH ₂ -S-, -CH ₂ -S-CH _2- , -CH ₂ CH ₂ -S-, -CH ₂ -S-CH ₂ CH _2- , -CH ₂ CH ₂ -S-CH _2- , -CH ₂ CH ₂ CH ₂ -S-, -CH ₂ -S-CH ₂ CH ₂ CH _2- , -CH ₂ CH ₂ -S-CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ -S-CH _2- , -CH (CH ₂ ) CH-, -C (CH ₂ CH ₂ )-, -CH ₂ CO-, -CH ₂ CH ₂ CO-,- CH (CH ₃ ) CH ₂ CO-, -CH (OH)-, -C (OH) (CH ₃ )-, -CH (F)-, -CH (Br)-, -CH (Br) CH (Br )-, -CH = CH-, -CH ₂ CH = CH-, -CH = CHCH _2- , -CH = CH-O-, -CH = CH-S- and -CH = CHCO- Which one is a photo-acid generator. The method of claim 1,
The photoacid generator, wherein the moiety represented by the following formula (3) which is the anion part of the compound represented by the formula (1) is any one selected from the group consisting of the following formula 1-i to 1-xx.
[Formula 3]

[Formula 1-i to 1-xx]

A first step of dissolving a compound represented by Formula 8 in a solvent and reacting with a reducing agent to obtain a compound represented by Formula 6,
A second step of reacting the compound represented by Formula 7 with the compound represented by Formula 6 under a basic catalyst to obtain a compound represented by Formula 4, and
A third step of obtaining a compound represented by the following formula 1 by the substitution reaction of the compound represented by the formula (4) and the compound represented by the formula (5)
Method of producing a photoacid generator represented by the following formula (1) comprising a.
[Formula 8]

[Formula 6]

[Formula 7]

[Formula 4]

[Formula 5]

[Chemical Formula 1]

(In Formula 1, Formula 4, Formula 5, Formula 6, Formula 7 and Formula 8,
R ₆ is an alkyl group,
Q ₁ , Q ₂ and Q ₅ are each independently a halogen atom,
Y is any one selected from the group consisting of a cycloalkyl group having 3 to 30 carbon atoms and a cycloalkenyl group having 3 to 30 carbon atoms,
X is any one selected from the group consisting of alkanediyl, alkenediyl, NR ', S, O, CO and combinations thereof, wherein R' is any one selected from the group consisting of hydrogen and alkyl groups,
N is an integer of 0 to 5,
A + is an organic counterion,
M + is any one selected from the group consisting of Li +, Na + and K +,
Z- is (OSO ₂ CF ₃ )-, (OSO ₂ C ₄ F ₉ )-, (OSO ₂ C ₈ F ₁₇ )-, (N (CF ₃ ) ₂ )-, (N (C ₂ F ₅ ) ₂ )-, (N (C ₄ F ₉ ) ₂ ), (C (CF ₃ ) ₃ )-, (C (C ₂ F ₅ ) ₃ )-, (C (C ₄ F ₉ ) ₃ )-, F -, Cl-, Br-, I-, BF _4- , AsF ₆ -and PF ₆ -is any one selected from the group consisting of A compound represented by the following formula (4).
[Formula 4]

(In Formula 4,
Y is any one selected from the group consisting of a cycloalkyl group having 3 to 30 carbon atoms and a cycloalkenyl group having 3 to 30 carbon atoms,
Q ₁ and Q ₂ are each independently a halogen atom,
X is any one selected from the group consisting of alkanediyl, alkenediyl, NR ', S, O, CO and combinations thereof, wherein R' is any one selected from the group consisting of hydrogen and alkyl groups,
N is an integer of 0 to 5,
M + is any one selected from the group consisting of Li +, Na + and K +) A chemically amplified resist composition comprising the photoacid generator according to any one of claims 1 to 5.