TW201414712A - Photoacid generator and preparing method thereof and resist composition and compound comprising same - Google Patents

Abstract

The present invention involves an photoacid generator which suppresses diffusion of acid to decrease line edge roughness while increasing acid yield to improve photosensitivity significantly, especially in formation of photographic pattern by utilizing EUV, and a composition comprising the same. The photoacid generator is shown as formula 1 below: In the formula 1, each of substituents is defined as the specification.

Description

Photoacid generator and resist composition containing the photoacid generator

The present invention relates to a novel photoacid generator capable of suppressing acid diffusion and capable of reducing line edge roughness while increasing acid yield and remarkably increasing the sensitivity of a resist, and a resist composition containing the photoacid generator.

Recently, ArF immersion in lithography technology, that is, HVM (high volume manufacturing) which is dependent on immersion lithography, is booming, and technology for achieving line widths below 50 nm is being mainly developed. . In addition, as the candidate technology that is expected to become the next-generation optical technology, the lithography technology using EUV (extreme infrared) is receiving much attention.

EUV lithography is a new generation of technology that is mainly researched to achieve patterns below 30 nm. In addition to defects in energy power or masks, it is expected to be commercialized in all aspects. International semiconductor technology The International Technology Roadmap for Semiconductors predicts that HVM will be implemented using this technology around 2015.

However, from the side of the resist of EUV lithography, in order to achieve technical success such as KrF or ArF, there are still many problems to be solved. These include the lack of photon necessary to embody the pattern and the problems associated with the problem. Unlike KrF or ArF lithography, EUV light is absorbed by all materials, so the path of light needs to be carried out under vacuum. The mask also needs to use a multilayer film that does not have translucency, and is irradiated to the resist by reflection. Thus, a high energy source is required in this process, requiring as high a light sensitivity as possible for the resist.

Thus, in order to solve the problem of achieving a pattern by low acid yield caused by a small amount of photons as described above, an acid value-increasing agent capable of exhibiting high acid yield under the same photo-sensing condition is being developed in large numbers. (acid amplifier).

Prior art literature

Patent Document 1: Korean Patent No. 1054485 (authorized by 2011.07.29)

Patent Document 2: Korean Laid-Open Patent Publication No. 2010-0064006 (published on 2010.06.14)

Patent Document 3: Korean Laid-Open Patent Publication No. 2011-0090825 (published on 2011.08.10)

Patent Document 4: Korean Laid-Open Patent Publication No. 2011-0095168 (published on 2011.08.24)

It is an object of the present invention to provide a reduction in acid diffusion and a reduction in line edge roughness while increasing the acid yield and significantly increasing the photosensitivity of the resist, especially when patterning using far infrared (EUV) lithography can be significantly improved. A photoresist acid photoreceptor (hereinafter referred to as PGA).

Another object of the present invention is to provide a resist containing the photoacid generator Agent composition.

In order to achieve the above object, a photoacid generator according to an embodiment of the present invention is a compound having the structure of the following Chemical Formula 1:

In the above Chemical Formula 1, V ₁ and V ₂ are each independently a halogen group; W ₁ and W ₂ are each independently a hydrogen atom or a halogen group; and X is selected from an alkyl group, an alkenyl group, NR', S, O. a group consisting of CO and a combination thereof, wherein R' is an alkyl group having 1 to 4 carbon atoms; and R ₁ and R ₂ are each independently an aryl group having 6 to 18 carbon atoms, wherein 1 - 5 or more hydrogen atoms selected from the group consisting of fluoroalkyl, halo, nitro, cyano, decyl and alkylcarbonyl are substituted or unsubstituted; R ₃ is hydrogen or carbon An alkyl group having an atomic number of from 1 to 4; a is an integer from 1 to 4, b is an integer from 0 to 5, c is an integer from 1 to 3, d is an integer from 1 to 3; and A+ is an organic counter ion.

Preferably, X is a carbonyl group.

Preferably, V ₁ and V ₂ are each independently a fluorine group; W ₁ and W ₂ are each independently a hydrogen atom or a fluorine group; X is a carbonyl group; and R ₁ and R ₂ are each independently selected from a trifluoromethyl group; An electron withdrawing group in the group consisting of a fluorine group, a chlorine group, a nitro group, a cyano group and an ethyl fluorenyl group; a substituted or unsubstituted aryl group having 6 to 30 carbon atoms; and R ₃ is a hydrogen atom or a methyl group; An integer of 1-3, b is an integer of 0-2, c is an integer of 1 or 2, and d is an integer of 1 or 2.

In the Chemical Formula 1, the anion moiety is more preferably selected from the group consisting of the following Chemical Formulas 4a to 4f.

Preferably, A+ is an organic counter ion selected from the group consisting of sulfoniums, iodoniums, phosphoniums, diazonium salts, pyridiniums and quinones, more preferably represented by the following chemical formula 5a or 5b Organic counter ions:

In Chemical Formula 5a and Chemical Formula 5b, X ₁ , X ₂ , Y ₁ and Y ₂ are each independently selected from a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an allyl group, and a carbon number of 1 to 10; a group consisting of a perfluoroalkyl group, a benzyl group, an aryl group having 6 to 30 carbon atoms, and a combination thereof; X ₁ and X ₂ and Y ₁ and Y ₂ may be bonded to each other to form a carbon atom. a saturated or unsaturated hydrocarbon ring of 3 to 30; and X ₃ , X ₄ , X ₅ , Y ₃ , Y ₄ , and Y ₅ are each independently selected from a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, a halogen group, an alkoxy group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, a thiophenoxy group, a thioalkoxy group having 1 to 30 carbon atoms, and having a carbon number of One of the group consisting of 1-20 alkoxycarbonylmethoxy groups and combinations thereof.

More preferably, A+ is an organic counter ion having a structure represented by the following Chemical Formula 6a to Chemical Formula 6v:

More preferably, the photoacid generator of Chemical Formula 1 is a group consisting of compounds of the following Chemical Formula 1a to Chemical Formula 1f:

According to another embodiment of the present invention, there is provided a process for producing a photoacid generator of the chemical formula 1, which comprises the step of reacting a compound represented by the following Chemical Formula 9 and the following Chemical Formula 10 under a base catalysis condition

In Chemical Formulas 9 and 10, V ₁ and V ₂ are each independently a halogen group; W ₁ and W ₂ are each independently a hydrogen atom or a halogen group; and X is selected from an alkyl group, an alkenyl group, NR', S, In the group consisting of O, CO and a combination thereof, R' is hydrogen or an alkyl group having 1 to 4 carbon atoms; Y is a halogen group; and R is 1 to 5 of a hydrogen atom. a substituted or unsubstituted aryl group having 6 to 18 carbon atoms selected from the group consisting of halogen, nitro, cyano, decyl, and alkylcarbonyl; R ₃ is hydrogen An atom or an alkyl group having 1 to 4 carbon atoms; a is an integer from 1 to 4, b is an integer from 0 to 5, c is an integer from 1 to 3, and d is an integer from 1 to 3; A+ is an organic counter ion .

According to another embodiment of the present invention, a resist composition containing the photoacid generator is provided.

According to another embodiment of the present invention, a resist composition for far infrared lithography containing the photoacid generator is provided.

According to another embodiment of the present invention, there is provided a compound represented by the following Chemical Formula 9:

Each substituent in Chemical Formula 9 is as described above.

The details of other embodiments of the invention are included in the following detailed description.

The photoacid generator according to the present invention contains a bulky anion moiety capable of suppressing acid diffusion, and PEB (post exposure baking) produces 1-3 acids per molecule, thereby increasing In addition, in the PEB, the hydroxyl group-containing compound formed by the decomposition of the anion portion forms a hydrogen bond with the acid to suppress acid diffusion, thereby reducing line edge roughness. In particular, the acid yield increasing effect is excellent, and the photosensitivity of the EUV pattern material can be remarkably improved, and as a result, the photoacid generator is particularly useful as an EUV lithography resist material.

1 is a 1H NMR chart of the compound ii prepared in Synthesis Example 1.

2 is a 1H NMR detection chart of the compound vi prepared in Example 2.

Hereinafter, the present invention will be described in detail by way of examples. But these implementations The examples are intended to be illustrative only, and the scope of the invention is not limited by the examples, but is defined by the scope of the appended claims.

In the case where there is no particular description in the specification, the halogen group means one selected from the group consisting of fluorine, chlorine, bromine and iodine.

In the case where there is no particular description in the specification, the alkyl group means a linear or branched alkyl group having 1 to 30 carbon atoms, and the alkyl group includes a monoalkyl group, a dibasic alkyl group and a tribasic alkyl group. . Specific examples of the alkyl group are a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group and the like, but are not limited thereto.

In the case where there is no particular description in the specification, the cycloalkyl group means a cycloalkyl group having 3 to 30 carbon atoms, and includes a monocyclic, bicyclic, tricyclic or tetracyclic ring. Further, it includes an adamantyl group, a norbornyl group, and a polycyclic cycloalkyl group having a norbornyl group.

In the case where there is no particular description in the specification, the aryl group means a compound containing a benzene ring and a derivative thereof, and for example, it may be toluene or xylene which are linked to a side chain of a benzene ring; and two or more benzene rings are passed through a single Bonded biphenyl, etc.; two or more benzene rings which are bonded via a cycloalkyl or heterocycloalkyl group as a medium, oxime, oxime, etc.; two or more benzene rings condensed by naphthalene or anthracene, etc. . In the case where there is no particular description in the specification, the aryl group means an aryl group having 6 to 30 carbon atoms.

In the present specification, all compounds or substituents may be substituted or unsubstituted unless otherwise specified. Here, substituted means that hydrogen is selected from a halogen atom, an alkyl group, a perfluoroalkyl group, a perfluoroalkoxy group, a hydroxyl group, a carboxyl group, a carbonyl group, a cyano group, a nitro group, an amino group, a thio group, an alkylthio group, or an alkyl group. Oxygen, mercapto, aldehyde, cycloalkyl, heterocyclyl, allyl, aryl, derivatives thereof, and combinations thereof One of the selected ones in the group instead.

In addition, in the present specification, "the combination thereof" means that two or more substituents are condensed and bonded by a single bond or a linker bond or two or more substituents, unless otherwise specified.

The present invention is characterized in that the photoacid generator contains a bulky anion moiety at the time of preparation to inhibit acid diffusion, and 1-3 acids per molecule in PEB, thereby increasing acid yield, and further, In the PEB, the hydroxyl group-containing compound formed by the decomposition of the anion portion forms a hydrogen bond with the acid to suppress acid diffusion, thereby reducing line edge roughness.

That is, the photoacid generator according to an embodiment of the present invention is an onium salt compound containing an anion portion and a cationic portion having an organic counter ion thereof, and can be represented by the following Chemical Formula 1:

In the anion portion of Chemical Formula 1, each of V ₁ and V _{2 is} independently a halogen group, and each of them is preferably a fluorine group.

W ₁ and W ₂ are each independently a hydrogen atom or a halogen group, and are each preferably independently a hydrogen atom or a fluorine group.

X is a group consisting of an alkyl group, an alkenyl group, NR', S, O, CO, and a combination thereof, in which case, R' is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. . X is preferably a carbonyl group (CO).

R ₁ and R ₂ are each independently one or more of 1-5 of a hydrogen atom selected from the group consisting of a fluoroalkyl group, a halogen group, a nitro group, a cyano group, a decyl group, and an alkylcarbonyl group. The electron-substituted or unsubstituted aryl group having 6 to 18 carbon atoms; preferably selected from the group consisting of the following chemical formulas 2a to 2e:

In Chemical Formula 2a-2e, R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ are each independently selected from the group consisting of a fluoroalkyl group, a halogen group, a nitro group, a cyano group, a decyl group, and an alkylcarbonyl group. The electron withdrawing body is preferably an electron withdrawing body selected from the group consisting of a trifluoromethyl group, a fluorine group, a chlorine group, a nitro group, a cyano group and an ethyl fluorenyl group, and h is an integer of 0-5, i and p An integer of 0-3, wherein j, k, and l are each independently an integer of 0-4, and n, o, and q are each independently an integer of 0-2, but 0 i+j 5,0 k+l+m 5 and 0 n+o+p+q 5.

More preferably, each of R ₁ and R _{2 is} independently an electron-withdrawing body selected from the group consisting of the following chemical formulas 3a to 3d:

Further, in Chemical Formula 1, R ₃ is hydrogen or an alkyl group having 1 to 4 carbon atoms, preferably hydrogen or methyl.

Further, a is an integer of 1-4, b is an integer of 0-5, c is an integer of 1-3, and d is an integer of 1-3; preferably, a is an integer of 1-3, and b is 0-2 An integer, c is an integer of 1 or 2, and d is an integer of 1 or 2.

Preferably, the anion moiety in Chemical Formula 1 is selected from the group consisting of Chemical Formula 4a to Chemical Formula 4f:

Further, in the cation portion of Chemical Formula 1, A is an organic counter ion, and is specifically selected from the group consisting of thioindigos, iodoniums, phosphoniums, diazonium salts, pyridiniums, and quinones. cation.

When A+ is a sulfonium-based organic counter ion, A+ is preferably an organic cation represented by the following Chemical Formula 5a or Chemical Formula 5b.

In Chemical Formulas 5a and 5b, X ₁ , X ₂ , Y ₁ and Y ₂ are each independently selected from a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an allyl group, and a total of 1 to 10 carbon atoms. One of a group consisting of a fluoroalkyl group, a benzyl group, an aryl group having 6 to 30 carbon atoms, and a combination thereof, X ₁ and X ₂ and Y ₁ and Y ₂ may be bonded to each other to form a carbon atom of 3 30 saturated or unsaturated hydrocarbon rings.

Further, X ₃ , X ₄ , X ₅ , Y ₃ , Y ₄ and Y ₅ are each independently selected from a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, a halogen group, and a carbon number of 1 to 30. Alkoxy group, aryl group having 6 to 30 carbon atoms, thiophenoxy group, thioalkoxy group having 1 to 30 carbon atoms, alkoxycarbonylmethoxy group having 1 to 20 carbon atoms And any of the groups of their combinations.

More preferably, A ⁺ is an organic counter ion having a structure represented by the following Chemical Formula 6a to Chemical Formula 6v:

Further, when A is an iodonium-based organic counter ion, A is preferably an organic counter ion represented by the following Chemical Formula 7a or Chemical Formula 7b: [Chemical Formula 7a]

In Chemical Formulas 7a and 7b, Z ₁₁ -Z ₁₃ and Z ₂₁ -Z ₂₃ are each independently selected from a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an allyl group, and a total of 1 to 10 carbon atoms. Any one of a group consisting of a fluoroalkyl group, an aryl group having 6 to 30 carbon atoms, and a combination thereof; and Z ₁₄ and Z ₂₄ are each independently an alkyl group selected from a halogen group and having 1 to 30 carbon atoms. a group, an alkoxy group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, a thiophenoxy group, a thioalkoxy group having 1 to 30 carbon atoms, and 1 carbon atom Any one of the group consisting of alkoxycarbonylmethoxy groups of -20 and combinations thereof.

More preferably, A ⁺ is an organic counter ion having a structure represented by the following Chemical Formula 8a to Chemical Formula 8i:

Among the organic counter ions, a sulfonium-based organic counter ion is more preferable.

More preferably, the photoacid generator of Chemical Formula 1 according to the present invention is selected from the group consisting of the compounds represented by the following Chemical Formula 1a to Chemical Formula 1f:

The photoacid generator of Chemical Formula 1 according to an embodiment of the present invention having the above structure can be produced by a method comprising the following compound of Chemical Formula 9 and a compound of the following Chemical Formula 10 under basic catalyst conditions; The step of carrying out the reaction.

In Chemical Formulas 9 and 10, A+, V ₁ , V ₂ , W ₁ , W ₂ , X, R ₃ and ad are as defined above.

R is an aryl group having 6 to 30 carbon atoms which is substituted or unsubstituted by an electron withdrawing electron in the hydrogen atom, R ₂ or R ₃ as defined above, and Y is a halogen group, preferably fluorine. base.

The following Reaction Scheme 1 shows a reaction step of preparation of a photoacid generator according to an embodiment of the present invention. The following Reaction Formula 1 is only an example for explaining the present invention, but the present invention is not limited thereto.

The photoacid generator (1b) of Chemical Formula 1 according to the present invention can be produced by reacting the compound 9a of Chemical Formula 9 with the sulfonium halide compound 10a of Chemical Formula 10, as shown in Reaction Scheme 1, wherein the compound of Chemical Formula 10 One to five hydrogen atoms are selected from the group consisting of a fluoroalkyl group, a halogen group, a nitro group, a cyano group, a decyl group, and an alkylcarbonyl group (which is R-(CO)-, where R is a carbon number of 1 One or more electron withdrawing groups in the group consisting of -8 alkyl groups are substituted or unsubstituted aryl groups having 6 to 18 carbon atoms. According to the reaction, the diol group in Chemical Formula 9 is reacted with a sulfonyl group of Chemical Formula 10 containing an aryl group substituted or unsubstituted by an electron withdrawing group.

The compound 9a of Chemical Formula 9 can also be produced by decomposing a dioxo group in the compound of Chemical Formula 11 by treating the compound of the following Chemical Formula 11 with an acid such as p-toluenesulfonic acid, or by using an alcohol solvent such as methanol. , the compound of chemical formula 11 below using an ion exchange resin (e.g., DOWEX ^TM 50W (manufactured Merck Chemicals ^{Corporation), S-Sepharose TM, SP} -Sepharose TM, S-Sephadex TM, SP-Sephadex TM, SP-Toyopearl TM 550C ^{, SP-Toyopearl TM 550M, SP} -Toyopearl TM 650C, SP-Toyopearl TM 650M, Trill Light TM SCR-B, Trill Light TM SCR-04 and the like to prepare a cation exchange resin) treatment method.

In Chemical Formula 11, A+, V ₁ , V ₂ , W ₁ , W ₂ , X, R ₃ and ad are as defined above, and L ₁ and L ₂ are each independently selected from an alkyl group having 1 to 10 carbon atoms. a cycloalkyl group having 3 to 30 carbon atoms, an aryl group having 3 to 30 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and a combination thereof, preferably each independently selected from the group consisting of In the group consisting of methyl, ethyl, cyclopropyl, phenyl, methoxy and ethoxy.

The compound of Chemical Formula 11 can also be produced by a production method comprising the following steps, as shown in the following Reaction Scheme 2, which comprises: a compound of the following Chemical Formula 11a (for example, trimethyl dioxane carboxylic acid) a step of reacting a compound of the following formula 11c with a carbonyl diimidazole of the formula 11b (step 1); a compound of the formula 11c prepared in the above step and a compound of the following formula 11d (for example) a step of preparing a compound of the following formula 11e by the reaction (1,1-difluoromethyl-2-hydroxyethylsulfonic acid, etc.); and a compound of the formula 11e prepared in the above step and the following A step of carrying out a reaction of a compound of Chemical Formula 11f (for example, triphenylsulfonium triflate or the like). At this time, a compound selected from the group consisting of N-bromodenimide, potassium iodide, sulfoxide, and a mixture thereof may be used instead of the carbonyldiimidazole of the chemical formula 11b.

[Reaction formula 2]

In the reaction formula 2, A+, V ₁ , V ₂ , W ₁ , W ₂ , R ₃ , X, L ₁ , L ₂ and ad are as defined above; and the M+ is selected from the group consisting of Li+, Na+ and K+. One of the group; the Q ₁ is an imidazolyl group; the Q ₂ - is selected from the group consisting of (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 - one of the group consisting of.

At this time, in the above Reaction Scheme 2, the chemical formula 11b may be a compound selected from the group consisting of N-bromosylimine, potassium iodide, sulfoxide, and a mixture thereof in place of the carbonyl diimidazole. When these compounds are reacted with the compound of Chemical Formula 11a, a compound of Chemical Formula 11c in which Q ₁ is a halogen group selected from the group consisting of fluorine, chlorine, bromine and iodine can be obtained.

In the above Reaction Scheme 1, the compound 10a of Chemical Formula 10 may be a sulfonium halide compound containing 1-5 of the hydrogen atoms selected from a fluoroalkyl group, a halogen group, a nitro group, and a cyano group. a substituted or unsubstituted aryl group having 6 to 18 carbon atoms in the group consisting of a methyl group and an alkylcarbonyl group, and specifically, bis(trifluoromethylbenzenesulfonate) may be used. (bis) bis trifluoromethyl benzene sulfonyl chloride or trifluoromethyl benzene sulfonyl chloride.

Further, the basic catalyst may be one selected from the group consisting of triethylamine, diethylamine, pyridine, diethylisopropylamine, and a combination thereof.

When the compound of the chemical formula 9 and the chemical formula 10 in the reaction formula 1 is reacted, in order to deplete the both compounds to improve the reaction efficiency, it is preferred that the compound of the chemical formula 9 and the compound of the chemical formula 10 are 1:1. The reaction was carried out at a molar ratio of 1:3.

Further, in the compound of Chemical Formula 9 and the basic catalyst, in order to shorten the reaction time and easily remove the residual basic catalyst, it is preferred to carry out the reaction at a molar ratio of 1:1 to 1:4.

The reaction in the reaction formula 1 can be carried out in a reaction solvent. Specifically, the reaction solvent may be selected from the group consisting of esters, ethers, lactones, ketones, amines, alcohols, and combinations thereof, preferably selected from the group consisting of dichloromethane, chloroform, and Ethyl chloride, acetonitrile, toluene, dimethylformamide, tetrahydrofuran, dimethylformamidine The amine, dimethyl hydrazine is one of the group consisting of them.

Specifically, the reaction is carried out by dissolving the basic mixture of the compound of Chemical Formula 9 and the compound of Chemical Formula 10 in the reaction solvent to prepare a reaction mixture, and then stirring the reaction mixture, and adding the basicity The process of the catalyst is carried out.

At this time, it is preferred that the stirring step is carried out at 20 ° C to 120 ° C for 1-4 hours, which is advantageous for increasing the yield of the product and forming a minimum by-product.

After the reaction end of the reaction mixture is quenched, the obtained reactant is crystallized according to a usual method to obtain the photoacid generator of the chemical formula 1.

According to the above production method, the photoacid generator of Chemical Formula 1 can be produced by an efficient and simple method using the compound of Chemical Formula 9.

Thus, according to another embodiment of the present invention, there is further provided the compound of the Chemical Formula 9 for use in the preparation of the photoacid generator of Chemical Formula 1.

Further, when the photoacid generator of Chemical Formula 1 prepared by the above-described production method is used for a resist, it exhibits an effect of suppressing acid diffusion and increasing acid yield by a mechanism shown by the following Reaction Formula 3 after light irradiation. .

The following Reaction Formula 3 schematically shows the effect of reducing the acid diffusion with exposure of the photoacid generator according to the present invention. This is only for the purpose of illustrating the invention, and the invention is not limited thereby.

[Reaction formula 3]

Specifically, when the photoacid generator A of the present invention is irradiated with light, acid B is formed by cation decomposition. At this time, the formed acid B is very bulky and the diffusion speed is slow, and as a result, the line edge roughness can be reduced.

Further, after performing post exposure baking (PEB) in the resist process, the acid B is decomposed to form compound C and two D. At this time, both the generated C and the two D compounds act as an acid and the amount of the acid increases, and as a result, it can be used as an acid value-enhancing agent when used for EUV corrosion, thereby improving low acid yield.

Further, the compound C acts as an acid as described above, and contains two hydroxyl groups to suppress acid diffusion caused by hydrogen bonding, thereby further reducing line edge roughness.

The photoacid generator according to the present invention is suitable for use in a resist due to molecular weight It is too large to be used in a large amount, but in fact, three acids are generated after light irradiation, and a small amount of use can also solve the problem of low acid yield and increased line edge roughness caused by the small photon number of EUV.

Thus, according to another embodiment of the present invention, a resist composition containing the photoacid generator is provided, and in particular, a composition for an EUV resist is provided.

Specifically, the resist composition contains the photoacid generator, a base polymer, and a solvent.

The photoacid generators are the same as described above, and may be used singly or in combination of two or more. Further, the photoacid generator is contained in an amount of from 0.3 to 15 parts by weight, preferably from 0.5 to 10 parts by weight, more preferably from 2 to 10 parts by weight, per 100 parts by weight of the polymer solid component. When the content of the photoacid generator exceeds 15 parts by weight, the perpendicularity of the pattern is remarkably lowered; when it is less than 0.3 parts by weight, the plasticity of the pattern may be lowered.

The raw material polymer for a resist can be used as long as it is used as a raw material resin in forming a resist film, and is not particularly limited. Specific examples are that the raw material polymer for resist may be selected from the group consisting of: (meth) acrylate polymer; (α-trifluoromethyl) acrylate-maleic anhydride copolymer; a cycloolefin-maleic anhydride copolymer; a polynorbornene; a polymer compound obtained by ring-opening metathesis reaction of a cycloolefin; a polymer compound obtained by adding a hydrogen to a polymer obtained by ring-opening metathesis reaction of a cycloolefin; hydroxystyrene And a derivative of (meth) acrylate; selected from the group consisting of styrene, vinyl naphthalate, vinyl anthracene, vinyl anthracene, hydroxyvinyl naphthyl ester, hydroxyvinyl anthracene, indene, hydroxy anthracene, anthracene a polymer compound obtained by copolymerizing any one of an alkene and a norbornadiene; a phenol resin; and a mixture thereof.

The base polymer contains 3 to 20% by weight based on the total weight of the resist composition. The content of the polymer is less than 3% by weight, the viscosity of the composition is too low to form a film of a desired thickness, and the pattern loss is severe due to a relatively large amount of the photoacid generator; more than 20% by weight, the film The thickness is too thick, the transmittance of radiation is lowered, and it is difficult to obtain a vertical pattern.

In order to obtain a uniform and flat resist coating film, it is preferred to dissolve the polymer and photoacid generator in a solvent having an appropriate evaporation rate and viscosity. Solvents which can be used in the present invention are ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, methoxyethyl acetate, ethoxyethyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether. Esters such as acetate, propylene glycol monopropyl ether acetate; methyl isopropanone, cyclohexanone, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, 2-heptanone, ethyl lactate, γ-butyl A ketone such as a lactone may be used alone or in combination of two or more.

The solvent can be appropriately adjusted in accordance with physical properties of the solvent, that is, volatility, viscosity, and the like, so that a uniform resist film can be formed.

Further, the resist composition of the present invention may further contain an additive for the purpose of improving coatability and the like.

The additive is not particularly limited as long as it is an additive generally used in a resist composition, and may specifically be an alkali dissolution inhibitor, an acid scavenger, a surfactant, etc., and may contain one or a mixture thereof. Two or more additives.

The alkali dissolution inhibitor is as long as it is an alkali solution generally used for a resist composition Any inhibitor can be used, and specifically, it may be a phenol or a carboxylic acid derivative or the like.

The acid scavenger can prevent the diffusion phenomenon of the acid generated by the photoacid generator from diffusing to the resist film due to light irradiation, and suppress the chemical reaction of the unexposed portion. The use of such an acid scavenger can improve the storage stability of the photosensitive resin composition, and at the same time further improve the resolution of the resist, and can also suppress the line of the resist pattern caused by the change in time (PED) between exposure processes. Wide change.

As the acid scavenger as described above, a basic compound can be used, specifically, ammonia, methylamine, isopropylamine, n-hexylamine, cyclopentylamine, methylenediamine, ethylenediamine, dimethylamine, diiso) can be used. Propylamine, diethyldiamine, N,N-dimethyldiamine, N,N-dimethylethylenediamine, trimethylamine, triethylamine, N,N,N',N'-tetramethyl Methylenediamine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethyltetraethylpentamine, dimethylethylamine, methyl b Propylamine, benzylamine, phenylethylamine, benzyldimethylamine, tetramethylammonium hydroxide, aniline, N,N-dimethyltoluidine, triphenylamine (acid scavenger), p-phenylenediamine, Pyrrole, oxazole, isoxazole, thiazole, isoisothiazole, imidazole, pyrazole, pyrroline, pyrrolidine, imidazoline derivative, pyridine derivative, pyridazine derivative, pyrimidine derivative, pyrazine derivative, pyridyl An oxazoline derivative, a pyrazolidine derivative, an acridine derivative, a pyridazine derivative, an amine such as morpholine; an aminobenzoic acid, an anthracene carboxylic acid, an amino acid derivative (for example, nicotinic acid, alanine, fine) Acid, aspartic acid, etc.), 3-pyridine sulfonic acid, p-toluenesulfonate Nitrogen-containing compounds such as pyridine, 2-hydroxypyridine, aminomethylphenol, 2,4-quinolinediol, 2-(2-hydroxyethyl)pyridine, 1-(2-hydroxyethyl)acridine; Amine, N-methylformamide, N,N-dimethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, acetamide, benzo a guanamine derivative such as guanamine; or phthalimide, amber An imine derivative such as an imine or a maleimide.

The acid scavenger is contained in an amount of from 0.01 to 5 parts by weight, preferably from 0.1 to 1 part by weight, per 100 parts by weight of the solid content of the polymer. If the content of the acid scavenger is less than 0.01 parts by weight, the influence of the delay time after exposure is greater, which affects the shape of the pattern; if it is more than 5 parts by weight, the resolution and photosensitivity may be lowered.

The surfactant is used for improving coating properties, developing properties, etc., and specifically may be polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene (polyoxyethylene) Polyoxyethylene), polyethylene glycol dilaurate, etc., but is not limited thereto.

The resist composition of the present invention having the composition as described above contains a photoacid generator having an acid diffusion suppressing effect, and can reduce line edge roughness caused by acid diffusion of non-exposure/exposure adjacent portions when a resist film is formed. .

Hereinafter, the embodiments of the present invention will be described in detail so as to be easily implemented by those skilled in the art. However, the invention may be embodied in a variety of different forms and is not limited to the embodiments described herein.

In a round bottom flask, 10 g of the compound i was dissolved in 100 ml of dichloroethane to prepare a solution, the solution was stirred, the reaction temperature was set to 55 ° C using an oil bath, and 0.5 g of a catalyst amount of p-toluene was added to the solution. The sulfonic acid was stirred for 3 hours. The end point of the reaction was determined by ¹ H NMR to give 7 g of compound ii.

¹ H NMR (CDCl ₃ , internal standard: tetramethyl decane): (ppm) 1.00 (s, 3H), 3.6 (d, 2H), 3.8 (d, 2H), 4.65 (t, 2H), 7.8 (m) , 15H)

Example 1

5 g of the compound ii prepared in the synthesis example 1 was dissolved in 50 ml of dichloroethane to prepare a solution, and 5.7 g of bis(trifluoromethyl)benzenesulfonium chloride compound iii was added to the solution at room temperature. Stir. At this time, 1.7 g of a basic catalyst triethylamine was added dropwise with stirring.

The end of the reaction was confirmed by TLC and ¹ H NMR. After the reaction was terminated, the obtained mixture was washed three times with distilled water. The obtained organic substance was subjected to distillation under reduced pressure to remove the solvent, and dried in vacuo to give 5.5 g of Compound iv.

¹ H NMR (CDCl ₃ , internal standard: tetramethyl decane): (ppm) 1.20 (s, 3H), 3.6 (d, 2H), 4.2 (d, 2H), 4.6 (t, 2H), 7.8 (m, 15H), 8.0 (s, 2H), 8.1 (s, 4H)

Example 2

5 g of the compound ii prepared in the synthesis example 1 was dissolved in 50 ml of dichloroethane to prepare a solution, and 4.5 g of trifluoromethylbenzenesulfonate compound v was added to the solution, followed by stirring at normal temperature. At this time, 1.7 g of a basic catalyst triethylamine was added dropwise with stirring.

The end of the reaction was confirmed by TLC and ¹ H NMR. After the reaction was terminated, the obtained mixture was washed three times with distilled water. The obtained organic substance was subjected to distillation under reduced pressure to remove the solvent, and dried in vacuo to give 6 g of compound vi.

¹ H NMR (CDCl ₃ , internal standard: tetramethyl decane): (ppm) 1.20 (s, 3H), 3.4 (d, 2H), 3.8 (d, 2H), 4.8 (t, 2H), 7.7 (d) , 4H), 7.9 (d, 4H), 7.6~8.0 (s, 15H)

Experimental example

A resist pattern was formed using the photoacid generators prepared in the above Examples 1 and 2, and various evaluations were performed on the prepared resist pattern.

Specifically, a compound represented by the following Chemical Formula 12 as a raw material resin (Mw: 8500 g/mol, Mw/Mn: 1.75, molar ratio (x: y: z: w) of each repeating unit: 1:1: 1:1) 100 parts by weight, according to the content shown in Table 1 below The compound prepared in the illustrated Examples 1 and 2 as a photoacid generator and 0.5 part by weight of tetramethyl ammonium hydroxide as a basic additive were dissolved in 1000 parts by weight of propylene glycol monoethyl ether acetate ( In a propyleneglycol monoethyl ether acetate (PGMEA), a 0.2 μm membrane screening procedure was then used to prepare a resist composition.

The obtained resist composition was applied onto a substrate by a spin coat, and dried at 110 ° C for 90 seconds to form a coating film having a thickness of 0.20 μm. The formed coating film was exposed to light using an ArF excimer laser stepper (prism numerical aperture: 0.78), and then heat-treated at 110 ° C for 90 seconds. Next, development was carried out for 40 seconds using a 2.38 wt% aqueous solution of tetramethylammonium hydroxide, followed by washing and drying to form a resist pattern.

Various evaluations were performed on the prepared resist pattern, and the results are shown in Table 1 below.

The photosensitivity in Table 1 below is the exposure amount formed by the line width and pitch (L/S) pattern of 0.10 μm formed after development at a line width of 1 to 1, which is the optimum exposure amount, and the exposure amount is In the case of photosensitivity, the size of the smallest pattern of development is taken as the resolution.

Further, for LWR (line width roughness), the roughness of the line width and pitch (L/S) pattern of 0.10 μm formed after development was observed, and LWR was measured (the smaller the value, the LWR) The more excellent).

The amount of the photoacid generator in Table 1 is a part by weight relative to 100 parts by weight of the raw material resin, and 30 parts by weight of triethylamine is added as a basic quencher with respect to 100 parts by weight of the photoacid generator ( Base quencher) for evaluation.

As is apparent from the results of Table 1, the resist composition prepared in Example 1-3 was significantly superior in sensitivity, resolution, and LWR characteristics to the resist composition prepared in Comparative Example 1. .

The preferred embodiment of the present invention has been described in detail above, but the present invention The scope of the invention is not limited by the scope of the invention, and various modified modifications of the basic concept of the invention as defined in the appended claims are also within the scope of the invention.

Claims (12)

A photoacid generator, as shown in the following Chemical Formula 1: In Chemical Formula 1, V ₁ and V ₂ are each independently a halogen group; W ₁ and W ₂ are each independently a hydrogen atom or a halogen group; and X is selected from an alkyl group, an alkenyl group, NR', S, O, In the group consisting of CO and a combination thereof, R' is an alkyl group having 1 to 4 carbon atoms; and R ₁ and R ₂ are each independently 1 to 5 of a hydrogen atom selected from a fluoroalkyl group and a halogen. One or more electron withdrawing groups in the group consisting of a group consisting of a nitro group, a cyano group, a decyl group and an alkylcarbonyl group, substituted or unsubstituted aryl group having 6 to 18 carbon atoms; and R ₃ is hydrogen or a carbon atom. A number of 1-4 alkyl groups; a is an integer from 1 to 4, b is an integer from 0 to 5, c is an integer from 1 to 3, d is an integer from 1 to 3; and A+ is an organic counterion. The photoacid generator according to claim 1, wherein X is a carbonyl group. The photoacid generator according to claim 1, wherein V ₁ and V ₂ are each independently a fluorine group; W ₁ and W ₂ are each independently a hydrogen atom or a fluorine group; X is a carbonyl group; R ₁ And R ₂ are each independently substituted or unsubstituted with an electron withdrawing group selected from the group consisting of a trifluoromethyl group, a fluorine group, a chloro group, a nitro group, a cyano group and an ethyl fluorenyl group, and the number of carbon atoms is 6-30. R ₃ is a hydrogen atom or a methyl group; an integer of 1-3, b is an integer of 0-2, c is an integer of 1 or 2, and d is an integer of 1 or 2. The photoacid generator according to claim 1, wherein in the chemical formula 1, the anion moiety is selected from the group consisting of the following chemical formula 4a to chemical formula 4f: (4e) (4f). The photoacid generator according to claim 1, wherein A+ is a group selected from the group consisting of thioindigos, iodoniums, phosphoniums, diazonium salts, pyridiniums and quinones. Organic counter ions in the middle. The photoacid generator according to claim 1, wherein A+ is an organic counter ion represented by the following Chemical Formula 5a or Chemical Formula 5b: In Chemical Formula 5a and Chemical Formula 5b, X ₁ , X ₂ , Y ₁ and Y ₂ are each independently selected from a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an allyl group, and a carbon number of 1 to 10; a group consisting of a perfluoroalkyl group, a benzyl group, an aryl group having 6 to 30 carbon atoms, and a combination thereof; X ₁ and X ₂ and Y ₁ and Y ₂ may be bonded to each other to form a carbon atom. a saturated or unsaturated hydrocarbon ring of 3 to 30; and X ₃ , X ₄ , X ₅ , Y ₃ , Y ₄ and Y ₅ are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, and a halogen. a group, an alkoxy group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, a thiophenoxy group, a thioalkoxy group having 1 to 30 carbon atoms And one of the group consisting of alkoxycarbonylmethoxy having 1 to 20 carbon atoms and a combination thereof. The photoacid generator according to claim 1, wherein A+ is an organic counter ion having a structure represented by the following Chemical Formula 6a to Chemical Formula 6v: The photoacid generator according to claim 1, wherein the photoacid generator is selected from the group consisting of the following chemical formulas 1a to 1f: A process for producing a photoacid generator of the following Chemical Formula 1, comprising the steps of reacting a compound represented by the following Chemical Formula 9 and the following Chemical Formula 10 under a basic catalyst condition: In Chemical Formula 1, Chemical Formula 9, and Chemical Formula 10, V ₁ and V ₂ are each independently a halogen group; W ₁ and W ₂ are each independently a hydrogen atom or a halogen group; and X is selected from an alkyl group, an alkenyl group, and an NR group. In the group consisting of ', S, O, CO, and a combination thereof, R' is hydrogen or an alkyl group having 1 to 4 carbon atoms; Y is a halogen group; and R, R ₁ and R ₂ are each independently hydrogen. The number of substituted or unsubstituted carbon atoms of one or more electron-optic groups selected from the group consisting of 1-5 of a fluoroalkyl group, a halogen group, a nitro group, a cyano group, a decyl group and an alkylcarbonyl group is 6 An aryl group of -18; R ₃ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; a is an integer of 1 to 4, b is an integer of 0 to 5, c is an integer of 1 to 3, and d is 1 An integer of -3; and A+ is an organic counterion. A resist composition comprising the photoacid generator according to any one of claims 1 to 8. A resist composition for far infrared resist, characterized in that it contains The photoacid generator according to any one of the items 1 to 8. A compound as shown in the following Chemical Formula 9: In Chemical Formula 9, V ₁ and V ₂ are each independently a halogen group; W ₁ and W ₂ are each independently a hydrogen atom or a halogen group; and X is selected from an alkyl group, an alkenyl group, NR', S, O, A group consisting of CO and a combination thereof, R' is hydrogen or an alkyl group having 1 to 4 carbon atoms; R ₃ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; a is an integer of 1 to 4 , b is an integer from 0 to 5, c is an integer from 1 to 3, and d is an integer from 1 to 3; and A+ is an organic counter ion.