TWI643919B - Conductive polymer composition, coated article, patterning process, and substrate - Google Patents

Abstract

An object of the present invention is to provide an electroconductive polymer composition which is excellent in antistatic property, does not adversely affect a resist, and has excellent coating properties, and is applicable to a conductive polymer composition using lithography such as electron beam.

The solution is a conductive polymer composition containing a polyaniline-based conductive polymer (A) having a repeating unit represented by the following formula (1), a polyanion (B), and a betaine compound. (C); (wherein R ^A1 to R ^A4 each independently represent any one of a linear, branched or cyclic monovalent hydrocarbon group, a hydrogen atom or a halogen atom having 1 to 20 carbon atoms of a hetero atom; ^A1 and R ^A2 , or R ^A3 and R ^A4 may be bonded to each other to form a ring).

Description

Conductive polymer composition, covering product, pattern forming method, and substrate

The present invention relates to a conductive polymer composition containing a polyaniline-based conductive polymer, a covering material using the same, a pattern forming method, and a substrate. More specifically, the present invention relates to an antistatic charged conductive polymer composition suitable for use as a resistant in lithography using ultraviolet rays, electron beams, or the like, and an article having an antistatic film formed using the same, A pattern forming method using the conductive polymer composition and a substrate obtained by the pattern forming method.

Conventionally, in the process of semiconductor devices such as ICs and LSIs, microfabrication is performed by a lithography method using photoresist. It is a method in which the solubility of the film is significantly changed by photo-induced crosslinking or decomposition reaction of the film, and the resist pattern obtained by using a solvent or the like is used as a mask to etch the substrate. . In recent years, with the high integration of semiconductor components, it has been increasingly required to use high-precision micro-fabrication of short-wavelength light. work. The use of electron beam lithography, due to its short wavelength characteristics, continues to be developed as a next generation technology.

Regarding the problem unique to the use of electron beam lithography, a charging phenomenon (charge up) at the time of exposure can be cited. When the substrate to be subjected to electron beam exposure is coated with an insulating resist film, electric charges are accumulated on the resist film or in the film to be charged. As a result of this charging, the orbit of the incident electron beam is curved, resulting in a significant reduction in the accuracy of the drawing. Thus, an antistatic film coated on an electron beam resist has been discussed.

In order to reduce such a reduction in the accuracy of drawing, Patent Document 1 discloses a composition containing a composite of an aniline-based conductive polymer, a polybasic acid, and H ₂ O, and it is clearly described that an aniline-based conductive polymerization is carried out. The composite composed of the compound and the polybasic acid is 5 to 10% by mass, and can be subjected to a good spin coating film formation, and exhibits a sufficient antistatic effect at a film thickness of 150 nm, and can be formed by peeling with H ₂ O. Net anti-static film.

However, when an antistatic film is provided on the chemical amplification resist, the acid formed by the exposure is neutralized by the component in the antistatic film, and if it is a positive type, the exposed portion of the resist is insoluble at the time of development, and is negative. When the resist exposure portion is partially dissolved during development, or vice versa, if the acid component in the antistatic film is a positive type, the unexposed portion of the resist is partially dissolved at the time of development, and the resist is a negative type. The unexposed portion is insolubilized at the time of development, and the like, and the change in the shape of the resist or the change in sensitivity may be observed.

Since chemically amplified resists are not resistant to most organic solvents, the antistatic agents disposed on the resists are mostly aqueous. However The surface of the chemically amplified resist is hydrophobic, and it is difficult to apply a water-based antistatic agent, but a surfactant or the like is added, but a mixed layer is formed on the surface of the resist by adding a surfactant, thereby contributing to the mixed layer. There is a problem in the acid generated in the resist and the acid component in the antistatic film after the above-described drawing, and there are problems such as a change in the shape of the resist or a change in sensitivity.

Patent Document 2 discloses a conductive composition containing a complex composed of an acidic group-substituted polyaniline-based conductive polymer and a basic compound, and heat resistance in a high-temperature environment, such as application to an electrolytic capacitor or the like, is clearly described. , the effect of the improvement of conductivity.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] US Patent No. 5,370,825

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2014-15550

[Patent Document 3] Japanese Laid-Open Patent Publication No. 2008-133448

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2010-77404

In the composition described in Patent Document 1, an acid derived from a polybasic acid existing in a composite body composed of a polyaniline conductive polymer and a polybasic acid has a high acidity, and the antistatic effect is effective. However, it can be seen that the shape change or sensitivity change of the resist has a poor influence on the lithography.

The polyaniline-based conductive polymer of Patent Document 2 is not limited to a polybasic acid of another molecule described in Patent Document 1, but is limited to self-doping of an acidic substituent introduced into an aniline monomer forming a conductive polymer. The polyaniline-based conductive polymer does not form a composite with the aniline-based conductive polymer and the polybasic acid. Further, the acidic substituent on the aniline monomer and the amine group of the aniline are present in a ratio of 1:1. Therefore, in order to comply with the purpose of use, it is difficult to change the composition ratio of the amine group derived from the polyaniline-based conductive polymer and the polymerizable substituent derived from the acidic substituent, and the hydrophilicity of the polymer is not helpful. The existence ratio of the acidic group formed by the high-dispersion complex of H ₂ O is limited, and therefore, the polymer in the composition is liable to re-agglomerate, and when it is applied as an anti-charge film on the chemical amplification type resist, Problems such as defects.

The present invention has been made in view of the above circumstances, and is excellent in antistatic property, does not adversely affect a resist, and has excellent coatability, and is particularly suitable for use in electropretation using electron beam or the like. The polymer composition is for the purpose.

In order to solve the above problems, the present invention provides

A conductive polymer composition containing a polyaniline-based conductive polymer (A) having a repeating unit represented by the following formula (1), a polyanion (B), and a betaine compound (C) ;

(wherein R ^A1 to R ^A4 each independently represent any one of a linear, branched or cyclic monovalent hydrocarbon group, a hydrogen atom or a halogen atom having 1 to 20 carbon atoms of a hetero atom; ^A1 and R ^A2 , or R ^A3 and R ^A4 may be bonded to each other to form a ring).

When such a conductive polymer composition is excellent in antistatic property and does not adversely affect the resist, it has excellent coatability, and therefore can be used as a conductive film which can be applied to lithography using an electron beam or the like. Molecular composition.

In this case, the component (C) is preferably represented by the following formula (2).

(wherein R ^B1 to R ^B3 each independently represent a linear, branched or cyclic monovalent hydrocarbon group or a hydrogen atom which may be substituted by a hetero atom or may have a carbon number of 1 to 20; Further, R ^B1 and R ^B2 or R ^B1 and R ^B2 and R ^B3 may be bonded to each other to form a ring together with A ⁺ in the formula; A ⁺ is a hetero atom and represents a monovalent cation; k represents an integer of 1 to 8 L is a carbon atom or a hetero atom. When k is 2 or more, it may have two types; R ^B4 and R ^B5 represent a hydrogen atom, or a linear or branched carbon group having a carbon number of 1 to 20 interposing a hetero atom; a monovalent hydrocarbon group which is cyclic or cyclic; in addition, R ^B4 and R ^B5 may be bonded to each other to form a ring; B ^- is a monovalent anionic functional group, which means a carboxylic acid ion or a sulfonic acid ion).

When the conductive polymer composition of the present invention contains the betaine compound represented by the above formula (2) as the component (C), when the conductive polymer composition is used to form an antistatic film on the workpiece, The diffusion of the acid between the object to be processed and the antistatic film is suppressed, and the influence of the acid can be alleviated.

Further, in this case, the component (C) is preferably represented by the following formula (3).

(wherein, R ^B1 to R ^B5 , A ⁺ , L, and k are the same as described above).

When the conductive polymer composition of the present invention contains the betaine compound represented by the above formula (3) as the component (C), when the conductive polymer composition is used to form an antistatic film on the workpiece, Further, the diffusion of the acid between the object to be processed and the antistatic film is further suppressed, and the influence of the acid can be further alleviated.

Moreover, in this case, the component (B) preferably contains the following formula (4).

(wherein R ¹ is a hydrogen atom or a methyl group, R ² is a single bond, an ester group, or any one of an ether group or an ester group or a linear or branched carbon number of 1 to 12; Any one of the cyclic hydrocarbon groups, and Z is any one of a stretching phenyl group, a stretching naphthyl group, and an ester group, and a is 0 < a ≦ 1.0).

When the conductive polymer composition of the present invention contains the component represented by the above formula (4) as the component (B), the effects of the present invention can be further enhanced.

In addition, the content of the component (C) is preferably from 1 part by mass to 50 parts by mass based on 100 parts by mass of the composite of the component (A) and the component (B).

By setting the content of the component (C) in this manner, the diffusion of the acid from the antistatic film formed of the conductive polymer composition to the resist layer can be reduced, and the antistatic effect at the time of electron beam drawing can be maintained and the acidity can be reduced. A high resolution resist pattern can be obtained by the effects of shadowing. Further, based on the same effect, it is possible to obtain a resist processed body having less sensitivity variation for the duration of the film formation to the pattern development.

In addition, the content of the component (C) is preferably from 3 parts by mass to 10 parts by mass based on 100 parts by mass of the composite of the component (A) and the component (B).

By setting the content of the component (C) in this manner, the diffusion of the acid from the antistatic film formed of the conductive polymer composition to the resist layer can be further reduced, and the antistatic effect at the time of electron beam drawing can be maintained and the acid can be further reduced. A analytic higher resist pattern can be obtained for the effects of lithography. Further, based on the same effect, it is possible to obtain a resist processed body having less sensitivity variation for the duration of the film formation to the pattern development.

Moreover, in this case, it is preferable that the conductive polymer composition further contains a nonionic surfactant.

In this way, the wettability of the substrate or the like to the object to be processed can be improved.

In addition, the content of the nonionic surfactant is preferably from 1 part by mass to 50 parts by mass based on 100 parts by mass of the composite of the component (A) and the component (B).

As a result, the wettability of the surface of the resist is better, and the antistatic property is also sufficient.

Further, the conductive polymer composition can be used for the formation of an antistatic film.

Furthermore, the present invention provides a cover which is provided with an antistatic film formed using the conductive polymer composition on a workpiece.

The antistatic film formed of the conductive polymer composition of the present invention is excellent in antistatic property, and a high-quality cover can be obtained by covering such an antistatic film with various workpieces.

Further, in this case, the substrate to be processed may be a substrate having a chemically amplified resist film.

Since the conductive polymer composition of the present invention does not adversely affect the resist, the object to be processed which can be provided with the antistatic film formed of the conductive polymer composition of the present invention can be selected to be difficult to apply in the past. A substrate having a chemically amplified resist film.

Further, at this time, the substrate to be processed may be a substrate for obtaining a resist pattern by irradiating an electron beam with a pattern.

When the conductive polymer composition of the present invention is particularly suitable for use in lithography using an electron beam or the like, a resist pattern having high sensitivity, high resolution, and a good pattern shape can be obtained.

Furthermore, the present invention provides a pattern forming method comprising the steps of forming an antistatic film using the conductive polymer composition on the resist film having a substrate of a chemically amplified resist film, and e. The step of irradiating the pattern and the step of developing the image using an alkaline developing solution to obtain a resist pattern.

According to such a pattern forming method, charging phenomenon at the time of exposure can be prevented, and a resist pattern having high sensitivity, high resolution, and a good pattern shape can be obtained.

Further, in the present invention, there is provided a substrate having a resist pattern obtained by the pattern forming method.

According to the pattern forming method of the present invention, a substrate having a resist pattern having high sensitivity, high resolution, and a good pattern shape can be obtained.

As described above, the conductive polymer composition of the present invention is excellent in antistatic property and can be suitably used for antistatic purposes. Moreover, by covering the various processed objects with the antistatic film formed using the conductive polymer composition of the present invention, a high-quality cover product can be obtained.

Further, when the conductive polymer composition of the present invention is applied to a lithography method using a photoresist, it does not cause adverse effects such as insolubilization of a resist or sensitivity fluctuation, and is excellent in coatability, and therefore, it is particularly suitable. In the case of lithography using an electron beam or the like, a resist pattern having high sensitivity, high resolution, and a good pattern shape can be obtained.

Hereinafter, embodiments of the present invention will be described in detail, but the present invention is not limited thereto.

In the past, in recent years, in the process of semiconductor devices, the use of an antistatic film has been discussed. However, there is a problem in that an acid contained in a composition such as a conductive composition adversely affects a resist.

Therefore, the inventors of the present invention have made efforts to carry out research to solve the above problems, and have found that by using a betaine compound, it is excellent in antistatic property, does not adversely affect a resist, and has excellent coatability and is suitable for use in electrons. The present invention has been completed by a conductive polymer composition of lithography such as a bundle.

That is, the conductive polymer composition of the present invention is characterized by containing a polyaniline-based conductive polymer, a polyanion, and a betaine compound.

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

[(A) Polyaniline-based conductive polymer]

The conductive polymer composition of the present invention contains the polyaniline-based conductive polymer represented by the following formula (1) as the component (A).

(wherein R ^A1 to R ^A4 each independently represent any one of a linear, branched or cyclic monovalent hydrocarbon group, a hydrogen atom or a halogen atom having 1 to 20 carbon atoms of a hetero atom; ^A1 and R ^A2 , or R ^A3 and R ^A4 may be bonded to each other to form a ring).

The polyaniline-based conductive polymer is an organic polymer in which the main chain is an aniline or a derivative other than a para-substituent of aniline. Examples of the polymer having the same function include polypyrroles, polythiophenes, polyacetylenes, polyphenylenes, polyphenylenes, polyacenes, polythiophenesethylenes, and the like. .

However, based on high dispersibility of H ₂ O, filterability of dispersion, peelability to H ₂ O or alkali developing solution after film formation, low defect in lithography, ease of polymerization, and storage From the viewpoint of low re-coagulation and stability in air, a polyaniline-based conductive polymer is used as the component (A).

The polyaniline-based conductive polymer can also obtain sufficient conductivity in an unsubstituted state, but has high dispersibility to H ₂ O, low re-cohesiveness, filterability of the dispersion, and H ₂ after film formation. In the case where the peeling property of the O or alkali developing solution is improved and the defect of the lithography is reduced, it is more preferable to introduce a substituent. As the substituent, a functional group such as a halogen atom, an alkyl group, a carboxyl group, an alkoxy group, a hydroxyl group or a cyano group can be introduced.

Specific examples of the aniline monomer used for obtaining the polyaniline-based conductive polymer include aniline, 2-methylaniline, 3-methylaniline, 2-ethylaniline, 3-ethylaniline, and 2 -isopropylaniline, 2-tris-butylaniline, 2,3-dimethylaniline, 2,5-dimethylaniline, 2,6-dimethylaniline, 3,5-dimethylaniline, 2,6-Diethylaniline, 2,6-diisopropylaniline, 2,3,5,6-tetramethylaniline, 2-methoxyaniline, 3-methoxyaniline, 2-ethoxy Aniline, 3-ethoxyaniline, 3-isopropoxyaniline, 3-hydroxyaniline, 2,5-dimethoxyaniline, 2,6-dimethoxyaniline, 3,5-dimethoxy Aniline, 2,5-diethoxyaniline, 2-methoxy-5-methylaniline, 5-tributyl-2-methoxyaniline, 2-chloro-5-methylaniline, 2 - chloro-6-methylaniline, 3-chloro-2-methylaniline, 5-chloro-2-methylaniline, etc. may be used alone or in combination of two or more.

Wherein, selected from the group consisting of 2-methylaniline, 3-methylaniline, 2-ethylaniline, 3-ethylaniline, 2-isopropylaniline, 2-methoxyaniline, 3-methoxyaniline, a (co)polymer composed of one or two of 2-ethoxyaniline, 3-ethoxyaniline, 3-isopropoxyaniline, and 3-hydroxyaniline, based on a complex formed with a polyanion The viewpoint of dispersibility, electrical conductivity, reactivity, and product thermal stability in H ₂ O is applicable.

[(B) polyanion]

The conductive polymer composition of the present invention contains a polyanion as the component (B). The polyanion used in the conductive polymer composition of the present invention is a polymer having a plurality of anionic groups in one molecule, which can be obtained by polymerizing a monomer having an anionic group or a monomer having an anionic group and having no anion. Based on the method of monomer copolymerization. These monomers may be used alone or in combination of two or more. Further, after obtaining a polymer having no anionic group, it may be obtained by sulfonating a sulfonating agent such as sulfuric acid, fuming sulfuric acid or sulfamic acid. Further, by temporarily obtaining a polymer having an anionic group, it is further sulfonated to obtain a polyanion having a higher anionic group content.

Examples of the monomer constituting the polyanion used in the present invention include a sulfonic acid group, a fluorinated sulfonic acid group, a phosphoric acid group, or a carboxyl group, and the like. More specifically, it may, for example, be mentioned. Containing -O-SO ₃ ^- H ⁺ , -SO ₃ ^- H ⁺ , -CH(CF ₃ )-CF ₂ -SO ₃ ^- H ⁺ , -CF ₂ -SO ₃ ^- H ⁺ , -COO ^- H ⁺ , - A monomer having a strong acid group such as O-PO ₄ ^- H ⁺ or -PO ₄ ^- H ⁺ . Among these, from the viewpoint of the doping effect on the polyaniline-based conductive polymer, -SO ₃ ^- H ⁺ , -CH(CF ₃ )-CF ₂ -SO ₃ ^- H ⁺ , -CF ₂ -SO are preferred. ₃ ^- H ⁺ , -COO ^- H ⁺ . Further, it is preferred that the anion group be disposed adjacent to the main chain of the polyanion at a predetermined interval.

Examples of the sulfonic acid group-containing monomer include styrenesulfonic acid, allyloxybenzenesulfonic acid, methylallyloxybenzenesulfonic acid, and vinylsulfonic acid. Acid, allylsulfonic acid, methallylsulfonic acid, 2-(methacryloxy)ethanesulfonic acid, 4-(methacryloxy)butanesulfonic acid, isoprenesulfonic acid , 2-propenylamine-2-methylpropanesulfonic acid, 1,1,3,3,3-pentafluoro-2-methylpropenyloxypropane-1-sulfonic acid, 1,1-difluoro- 2-methylpropenyloxyethanesulfonic acid, 1,1,3,3,3-pentafluoro-2-(4-vinyl-benzylideneoxy)-propane-1-sulfonic acid, 1,1 -Difluoro-2-(4-vinyl-benzylideneoxy)-ethanesulfonic acid, benzyltrimethylammonium = 2-methylpropenyloxyethyl difluorosulfonate, and the like. These monomers may be used alone or in combination of two or more.

Alternatively, polystyrene, polymethylstyrene or the like may be polymerized and then sulfonated with a sulfonating agent such as sulfuric acid, fuming sulfuric acid or sulfamic acid to obtain a polyanion used in the present invention.

Further, Patent Document 3 and Patent Document 4 propose an acid generator which can produce a polymer type sulfonium salt having a fluorinated sulfonic acid at the α-position. The ytterbium salt of the fluorinated sulfonic acid bonded to the α-position of the polymer backbone is a super-strong superacid of sulfonic acid produced by photodecomposition of the cerium salt, by homopolymerizing or copolymerizing the repeating unit, The aforementioned polyanion can be obtained. Further, when the sulfonium salt of the polymer type is in the form of an alkali metal salt, an ammonium salt or an amine salt, it is preferred to add an inorganic acid or an organic acid such as sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid or perchloric acid, or use The cation exchange resin causes the solution to form an acid form.

Examples of the carboxyl group-containing monomer include ethylenically unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, 4-vinylbenzoic acid, and crotonic acid; and ethylene such as maleic acid, fumaric acid, and itaconic acid. Sexually unsaturated polycarboxylic acids and their anhydrides; partial esterified products of ethylenically unsaturated polycarboxylic acids such as methyl maleate and methyl itaconate; These monomers can be used individually or in groups The use of two or more kinds is more preferably used in combination with the above sulfonic acid monomer from the viewpoint of the doping effect on the polyaniline-based conductive polymer.

Examples of the phosphoric acid group-containing monomer include 3-chloro-2-acid type phosphorus oxypropyl (meth) acrylate and acid phosphoxy polyoxyethylene glycol mono (meth) acrylate. Mono (2-hydroxyethyl acrylate) acid phosphate, mono (2-hydroxyethyl methacrylate) acid phosphate, mono (2-hydroxypropyl acrylate) acid phosphate, mono (methacrylic acid 2 -Hydroxypropyl ester)acid phosphate, mono(3-hydroxyethyl acrylate) acid phosphate, mono(3-hydroxyethyl methacrylate) acid phosphate, diphenyl-2-propenyloxy group Ethyl phosphate, diphenyl-2-methylpropenyloxyethyl phosphate, and the like. These monomers may be used singly or in combination of two or more kinds, and it is more preferably used in combination with the above sulfonic acid monomer from the viewpoint of the doping effect on the polyaniline-based conductive polymer.

As the other monomer having no anionic group copolymerizable with the monomer having an anionic group, a well-known compound can be used without any limitation. For example, a conjugated diene monomer such as 1,3-butadiene, isoprene, 2-chloro-1,3-butadiene or 2-methyl-1,3-butadiene; An aromatic vinyl monomer such as styrene, α-methylstyrene or p-methylstyrene; methyl (meth)acrylate, ethyl (meth)acrylate or butyl (meth)acrylate; Ethylene unsaturated carboxylic acid alkyl ester monomer such as 2-ethylhexyl methacrylate; acrylamide, methacrylamide, N,N-dimethyl decylamine, N-methylol An ethylenically unsaturated carboxylic acid decylamine monomer such as acrylamide or the like; an ethylenically unsaturated carboxylic acid hydroxyalkyl ester monomer such as a hydroxyalkyl (meth) acrylate or a glycerol di(meth) acrylate; Vinyl carboxylate monomer such as vinyl ester; (meth)acrylonitrile, N-vinylpyrrolidone, (meth)acrylonitrile? Porphyrin, cyclohexylmaleimide, isopropylmaleimide, glycidyl (meth)acrylate, and the like.

The above monomer can be polymerized using, for example, an initiator to obtain a polyanion used in the present invention.

Further, sulfonation of polyether ketone (European Patent Application Publication No. 0041780 (A1) specification), sulfonation of polyetheretherketone (JP-A-2008-108535), sulfonate of polyether oxime Sulfation of polyphenylene, polyfluorene, and polyvinylcarbazole (Japanese Patent Laid-Open Publication No. 2010-514161), sulfonation of polyphenylene ether, and sulfonation of polysulfurized benzene (Japanese Patent Publication No. Hei 10-309449) The polyanion used in the present invention is obtained in the same manner.

Among the above polyanions, polyisoprene sulfonic acid, polyisoprene sulfonic acid-containing copolymer, polymethyl methacrylate sulfonate, and polymethacrylic acid sulfonic acid are preferably used from the viewpoint of conductivity. a copolymer of ethyl ester, poly(4-sulfonic acid butyl sulfonate), a copolymer containing poly(butyl 4-sulfonate methacrylate), polymethylallyloxybenzenesulfonic acid, Copolymer containing polymethylallyloxybenzenesulfonic acid, polystyrenesulfonic acid, copolymer containing polystyrenesulfonic acid, poly-1,1,3,3,3-pentafluoro-2-methylpropene a copolymer of decyloxypropane-1-sulfonic acid containing poly(1,1,3,3,3-pentafluoro-2-methylpropenyloxypropane-1-sulfonic acid, containing poly(1,1-di) a copolymer of fluoro-2-methylpropenyloxyethanesulfonic acid containing poly(1,1,3,3,3-pentafluoro-2-(4-vinyl-benzylideneoxy)-propane- Copolymer of 1-sulfonic acid, copolymer containing poly(1,1-difluoro-2-(4-vinyl-benzylideneoxy)-ethanesulfonic acid, 2-methyl polydifluorosulfonate Propylene methoxyethyl ester.

More preferably, it is polystyrenesulfonic acid, poly 1,1,3,3,3-pentafluoro-2-methyl Propylene methoxypropane-1-sulfonic acid, copolymer containing poly(1,1-difluoro-2-methylpropenyloxyethanesulfonic acid), containing poly(1,1,3,3,3-pentafluoro-) Copolymer of 2-(4-vinyl-benzhydryloxy)-propane-1-sulfonic acid containing poly(1,1-difluoro-2-(4-vinyl-benzylideneoxy)-B Copolymer of sulfonic acid, 2-methylpropenyloxyethyl ester of polydifluorosulfonic acid acetate, polysulfonic acid ethyl methacrylate, poly(4-sulfobutyl methacrylate).

Further, as the component (B), those represented by the following formula (4) can also be used:

(wherein R ¹ is a hydrogen atom or a methyl group, R ² is a single bond, an ester group, or any one of an ether group or an ester group or a linear or branched carbon number of 1 to 12; Any one of the cyclic hydrocarbon groups, and Z is any one of a stretching phenyl group, a stretching naphthyl group, and an ester group, and a is 0 < a ≦ 1.0).

In addition, the repeating unit represented by the above formula (4) preferably contains one or more selected from the group consisting of a1 to a4 represented by the following general formulae (4-1) to (4-4).

(wherein R ¹ is the same as described above, and a1, a2, a3, and a4 are 0≦a1≦1.0, 0≦a2≦1.0, 0≦a3≦1.0, 0≦a4≦1.0, respectively, and 0<a1+ A2+a3+a4≦1.0).

The degree of polymerization of the polyanion is preferably in the range of 10 to 100,000 monomer units, and more preferably in the range of 50 to 10,000, from the viewpoint of solvent solubility and conductivity. Further, the molecular weight of the polyanion is preferably from 5,000 to 1,000,000. When it is more than the above lower limit value, the polyanion easily forms a uniform solution; and if it is at most the above upper limit value, the conductivity is also better.

In the conductive polymer composition of the present invention, the polyanion is coordinated with the polyaniline-based conductive polymer to form a composite of a polyaniline-based conductive polymer and a polyanion.

(Method for producing a composite of a polyaniline conductive polymer and a polyanion)

The composite of the polyaniline-based conductive polymer and the polyanion can be added as a raw material of the polyaniline-based conductive polymer, for example, by mixing an aqueous solution of a polyanion or a polyanion in a water/ organic solvent mixed solution. An oxidizing agent is added for oxidative polymerization. When the polyanion is in the form of an alkali metal salt, an ammonium salt or an amine salt, it is preferred to add an inorganic acid or an organic acid such as sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid or perchloric acid in advance, or to form an acid by using a cation exchange resin. form.

As the oxidizing agent and the oxidation catalyst, a transition metal compound such as peroxodisulfate such as ammonium peroxodisulfate, sodium peroxodisulfate or potassium peroxydisulfate; iron chloride, iron sulfate or copper chloride; Silver oxide, oxygen A metal oxide such as a peroxide, a peroxide such as hydrogen peroxide or ozone, an organic peroxide such as benzamidine peroxide, or an oxygen gas.

As the reaction solvent used in the oxidative polymerization, water or a mixed solvent of water and a solvent can be used. The solvent used herein is preferably a solvent which can be mixed with water and which dissolves or disperses a polyanion or a polyaniline-based conductive polymer described later. For example, N-methyl-2-pyrrolidone, N,N'-dimethylformamide, N,N'-dimethylacetamide, dimethylammonium, hexamethylphosphonium can be mentioned. A polar solvent such as triamine, an alcohol such as methanol, ethanol, propanol or butanol, ethylene glycol, propylene glycol, dipropylene glycol, 1,3-butylene glycol, 1,4-butanediol, D-glucose, Polybasic aliphatic alcohols such as D-glucitol, isoprene diol, butane diol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, and the like a carbonate compound such as a vinyl carbonate or a propylene carbonate, a cyclic ether compound such as dioxane or tetrahydrofuran, a dialkyl ether, an ethylene glycol monoalkyl ether, an ethylene glycol dialkyl ether, or a propylene glycol single A chain ether such as an alkyl ether, a propylene glycol dialkyl ether, a polyethylene glycol dialkyl ether or a polypropylene glycol dialkyl ether; a heterocyclic compound such as 3-methyl-2-oxazolinone; or acetonitrile a nitrile compound such as glutaronitrile, methoxyacetonitrile, propionitrile or benzonitrile. These solvents may be used singly or in combination of two or more. The mixing ratio of the solvent-mixable water to water is preferably 50% by mass or less based on the entire reaction solvent.

The composite of the polyaniline-based conductive polymer and the polyanion thus obtained may be used as a fine particle by a homogenizer or a ball mill as needed.

Fine granulation is preferably carried out using a mixing disperser which imparts high shear force. As The mixing and dispersing machine may, for example, be a homogenizer, a high pressure homogenizer, a bead mill or the like, and among them, a high pressure homogenizer is preferred.

Specific examples of the high-pressure homogenizer include the product name Nanomizer manufactured by Yoshida Machinery Co., Ltd., the product name Microfluidizer manufactured by Powrex Co., Ltd., and the ULTIMAIZER manufactured by SUGINO MACHINE.

Examples of the dispersion treatment using a high-pressure homogenizer include a treatment of colliding a composite solution before the dispersion treatment with high pressure, a treatment of passing a hole or a slit at a high pressure, and the like.

Before or after the granulation, impurities may be removed by filtration, ultrafiltration, dialysis or the like, and purified by a cation exchange resin, an anion exchange resin, a chelating resin or the like.

Further, the total content of the polyaniline-based conductive polymer and the polyanion in the conductive polymer composition is preferably 0.05 to 10.0% by mass. When the total content of the polyaniline-based conductive polymer and the polyanion is 0.05% by mass or more, sufficient conductivity can be obtained. When the content is 5.0% by mass or less, a uniform conductive coating film can be easily obtained.

In addition, when the pH of the polyaniline-based conductive polymer and the polyanion is not adjusted in the state of the H ₂ O dispersion, the pH is usually from 1 to 2.5, and the strong acidity is exhibited. However, the antistatic film is coated with various types. In the case of the object to be processed, the pH is preferably in the range of 4 to 8 in view of the influence of the acid on the adjacent layer. When the pH is 4 or more and the pH is 8 or less, corrosion by acid and diffusion of acid into adjacent layers can be suppressed. When the coating is a resist, the resist is not easily damaged, and the pattern after development is also better.

The content of the polyanion is preferably in the range of 0.1 to 10 mols, more preferably in the range of 1 to 7 mols, based on the polyaniline-based conductive polymer 1 mol. When the anion group in the polyanion is 0.1 mol or more, the doping effect on the polyaniline-based conductive polymer is high, and sufficient conductivity can be ensured. Further, when the anion group in the polyanion is 10 mol or less, the content of the polyaniline-based conductive polymer is an appropriate amount, and sufficient conductivity can be obtained.

[(C) betaine compound]

The conductive polymer composition of the present invention contains a betaine compound as the component (C).

In the present invention, all known betain base compounds can be used.

Further, the betaine compound may be used alone or in combination of two or more.

As the betaine compound used in the present invention, it is preferably represented by the following formula (2):

(wherein R ^B1 to R ^B3 each independently represent a linear, branched or cyclic monovalent hydrocarbon group or a hydrogen atom which may be substituted by a hetero atom or may have a carbon number of 1 to 20; Further, R ^B1 and R ^B2 or R ^B1 and R ^B2 and R ^B3 may be bonded to each other to form a ring together with A ⁺ in the formula; A ⁺ is a hetero atom and represents a monovalent cation; k represents an integer of 1 to 8 L is a carbon atom or a hetero atom. When k is 2 or more, it may have two types; R ^B4 and R ^B5 represent a hydrogen atom, or a linear or branched carbon group having a carbon number of 1 to 20 interposing a hetero atom; a monovalent hydrocarbon group which is cyclic or cyclic; in addition, R ^B4 and R ^B5 may be bonded to each other to form a ring; B ^- is a monovalent anionic functional group, which means a carboxylic acid ion or a sulfonic acid ion).

In the formula (2), A ⁺ is a hetero atom and represents a monovalent cation. Examples of A ⁺ include a cesium ion, an ammonium ion, and the like.

B ^- is a monovalent anionic functional group representing a carboxylic acid ion or a sulfonic acid ion. B ^- forms an internal salt with A ⁺ present in the same molecule, or forms a salt with A ^{+ of} adjacent molecules between 2 molecules.

Further, as for the component (C), it is more preferably represented by the following formula (3):

(wherein, R ^B1 to R ^B5 , A ⁺ , L, and k are the same as described above).

Among the betaine compounds represented by the above formula (2), as the structure having a sulfonic acid ion, specifically, the following may be exemplified:

Further, specific examples of the structure of the betaine compound represented by the above formula (3) include the following:

In addition, the content of the betaine compound is preferably from 1 part by mass to 50 parts by mass, more preferably from 3 parts by mass to 10 parts by mass, per 100 parts by mass of the composite of the polyaniline-based conductive polymer and the polyanion. By setting the content of the betaine compound in this manner, the diffusion of the acid from the antistatic film formed of the conductive polymer composition of the present invention to the resist layer can be reduced, and the antistatic effect at the time of electron beam drawing can be maintained and the acid can be reduced. A high resolution resist pattern can be obtained for the effects of lithography. Further, based on the same effect, it is possible to obtain a resist processed body having less sensitivity variation for the duration of the film formation to the pattern development.

(surfactant)

In the present invention, a surfactant may be added to enhance the wettability to a workpiece such as a substrate. As a preferred surfactant, non-dissociation Subsystem surfactant. Specific examples thereof include polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene carboxylate, sorbitan ester, polyoxyethylene sorbitan ester, and acetylene glycol.

The content of the nonionic surfactant is preferably from 1 part by mass to 50 parts by mass, more preferably from 2 parts by mass to 20 parts by mass, per 100 parts by mass of the composite of the polyaniline-based conductive polymer and the polyanion. . When it is more than the above lower limit value, the wettability to the surface of the resist is more favorable, and if it is at most the above upper limit value, the antistatic property is sufficient.

In order to obtain the conductive polymer composition of the present invention, for example, a betaine compound may be further added by mixing a polyaniline-based conductive polymer and a polyanion complex, a solvent, a surfactant, or the like, and high-pressure homogenization may be applied as needed. Machine, etc., and further filtered by UPE filter.

The conductive polymer composition thus obtained can be applied to a workpiece such as a substrate to form an antistatic film. Examples of the coating method of the conductive polymer composition include coating by spin coating, spin coating, dipping, corner wheel coating, spray coating, roll coating, gravure printing, and the like. . After coating, an antistatic film can be formed by heat treatment using a hot air circulation furnace, a heating plate, or the like.

Examples of the object to be processed include a compound semiconductor wafer such as a glass substrate, a quartz substrate, a mask blank substrate, a resin substrate, a germanium wafer, a gallium arsenide wafer, and an indium phosphide wafer.

The cover which is covered with the antistatic film obtained by using the conductive polymer composition of the present invention may, for example, be provided with an antistatic film. A glass substrate, a resin film provided with an antistatic film, a resist substrate provided with an antistatic film, and the like.

In particular, since the conductive polymer composition of the present invention does not adversely affect the resist, the object to be processed is applicable to a substrate having a chemically amplified resist film; moreover, if it is used Better results can be obtained when the electron beam is irradiated to the pattern to obtain a substrate of the resist pattern.

Moreover, the present invention provides a pattern forming method comprising the steps of forming an antistatic film using the conductive polymer composition of the present invention on the resist film having a substrate of a chemically amplified resist film, The step of irradiating the pattern with the electron beam and the step of developing the image using the alkaline developing solution to obtain a resist pattern.

The pattern forming method may be carried out in accordance with a usual method in addition to the conductive polymer composition of the present invention, and may be subjected to heat treatment after exposure to perform development, and may be subjected to an etching step and a resist removal step. , other steps such as washing steps.

According to such a pattern forming method, charging phenomenon at the time of exposure can be prevented, and a resist pattern having high sensitivity, high resolution, and a good pattern shape can be obtained.

Further, in the present invention, there is provided a substrate having a resist pattern obtained by the pattern forming method.

Further, the present invention is designed for use in lithography using an electron beam or the like, and is excellent in antistatic property, ultraviolet lithography, anti-static use such as a film or glass, and the like.

[Examples]

Hereinafter, the present invention will be more specifically disclosed by way of Production Examples, Examples and Comparative Examples, but the present invention is not limited by the Examples.

In addition, the measurement methods and evaluation methods of each physical property are as follows:

The antistatic film in the following Examples 1 to 10 and Comparative Examples 1 to 4 and the spin coating system used as the resist film for the lower layer were subjected to a spin coater MS-A200 (manufactured by MIKASA Co., Ltd.). ). In addition, the positive type chemical amplification type resist is a positive type chemically amplified electron beam resist (a) manufactured by Shin-Etsu Chemical Co., Ltd. Further, a negative-type chemically amplified electron beam resist is manufactured by Shin-Etsu Chemical Co., Ltd. (b).

The positive chemical amplification inhibitor (a) and the negative chemical amplification resist (b) were formed by baking with a precision thermostat at 110 ° C for 240 seconds to remove the solvent. Examples 1 to 10 and Comparative Example 1 The anti-static film of ~4 is baked with a precision thermostat at 90 ° C for 90 seconds to remove the solvent. Further, the resist film thickness and the antistatic film thickness are determined by a spectroscopic ellipsometer VASE (manufactured by J.A. Woollam Co., Ltd.) whose incident angle is variable.

(filterability)

After preparing the conductive polymer composition of the following examples and comparative examples, a UPE filter (manufactured by Entegris Co., Ltd.) having a pore diameter of 0.5 to 0.050 μm was used for filtration, and a filter capable of filtering without clogging of the filter was examined. The aperture. In the following Examples 1 to 10 and Comparative Examples 1 to 4, the flow-through limits of the UPE filter subjected to filtration of the conductive polymer composition are shown in Table 1.

(pH measurement)

The pH of the conductive polymer composition of Examples 1 to 10 and Comparative Examples 1 to 4 was measured using a pH meter D-52 (manufactured by Tsukaku Seisakusho Co., Ltd.). The results are shown in Table 1.

(film formation)

The person who can form a uniform film is rated as ○, and the one which can measure the refractive index but the defect caused by the film-generating particle or the part which produces a streak is evaluated as X, and the evaluation is performed based on the standard. The evaluation results are shown in Table 1.

(water wash stripping)

10 μL of the conductive polymer composition was dropped on the film of the resist (a) or the resist (b) obtained by the film formation method, and heated at 90 ° C for 90 seconds with a precision thermostat, and then at room temperature in air. Leave for 2 minutes. The antistatic film formed by rinsing the ion exchange water filled in the washing bottle. When the antistatic film was peeled off within 10 seconds, it was rated as ○, and when it was more than 10 seconds and within 20 seconds, the peeling was evaluated as Δ, and the other unmeasurable persons were described as the cause, and the evaluation was performed based on the standard. The evaluation results are shown in Table 1.

(resist damage)

For the substrate after the water-repellent peelability evaluation, the color change of the substrate in which the base of the anti-static film was peeled off was evaluated as ○, the portion of the visible color change was rated as Δ, and the total visible color change was evaluated as ×, Benchmark Conduct an assessment. The evaluation results are shown in Table 1.

(surface resistivity)

The surface resistivity (Ω/□) of the antistatic film was measured using Hiresta-UP MCP-HT450 and pure J Box U Type Probe MCP-JB03 (manufactured by Mitsubishi Chemical Corporation). The results are shown in Table 1.

(Electron beam lithography evaluation and PCD (Post Coating Delay) evaluation)

The temporal change caused by the influence of the resist film from the conductive polymer film before irradiation was measured. The two-layer film of the resist film and the conductive polymer film which are applied by the method described below is placed in the electron beam drawing device for 7 days, 14 days, and 30 days after the film formation, as follows. The PEB pre-peeling procedure or the PEB post-peeling procedure of the conductive polymer film obtains a resist pattern. The sensitivity of the pattern width under the sensitivity was determined for the sensitivity of the resist and the conductive polymer film immediately after film formation.

‧PEB pre-peeling procedure assessment

(a) spin-coating of a positive-type chemical amplification resist on a 6-inch wafer using MARK VIII (Tokyo Electron Co., Ltd., Coater Developer Clean Track), and on a hot plate at 110 ° C, The film was baked to form a 150 nm resist film in 240 seconds. On the obtained resist-attached wafer, the conductive polymer composition was spin-coated with MARK VIII in the same manner as described above, and baked on a hot plate at 90 ° C for 90 seconds to prepare a conductive polymer. membrane. A wafer having a two-layer film provided with a resist film and a conductive polymer film was applied to the wafer immediately after the application, 7 days later, 14 days later, and 30 days later, according to the following method. First, the wafer immediately after coating was exposed using an electron beam exposure apparatus (Hitachi High-Technologies Co., Ltd., HL-800D acceleration voltage 50 keV), and then the pure polymer was rinsed for 15 seconds to conduct a conductive polymer. The film was peeled off and baked at 110 ° C for 240 seconds (PEB: post exposure bake), and further developed with an aqueous solution of 2.38 mass% of tetramethylammonium hydroxide. The wafer with the pattern prepared by observing the above-described empty SEM (scanning electron microscope) is capable of analyzing the exposure amount of the line and space of 400 nm by 1:1 as the optimum exposure amount (sensitivity) (μC/cm ² ). The minimum size at the optimum exposure amount is taken as the resolution. In addition, the resist pattern was obtained in the same manner for the wafers that passed the 7th, 14th, and 30th days after the coating was set, and the line and space of 400 nm were analyzed by 1:1 for the wafer immediately after the application. The exposure amount is used as the variation of the line width of the pattern under the optimum exposure amount (sensitivity) (μC/cm ² ). The results are shown in Table 2.

‧PEB post-peeling procedure assessment

A wafer coated with a two-layer film provided with a resist film and a conductive polymer film was produced in the same manner as the pre-PEB stripping procedure described above, and the wafer was passed through 7 days, 14 days, and 30 days after being separately applied. After the electron beam exposure, the pure water was rinsed for 15 seconds to peel off the conductive polymer film, that is, baking was performed at 110 ° C for 240 seconds (PEB: post exposure bake), and then 2.38 mass % of tetramethyl hydroxide was used. An aqueous solution of ammonium was developed to obtain a resist pattern. The change in the line width at the optimum exposure amount (sensitivity) (μC/cm ² ) was measured for the amount of exposure of the wafer immediately after the application was set to 1:1 with respect to the line and space of 400 nm. The results are shown in Table 3.

For the negative resist (b), the same evaluation as the above positive resist (a) was carried out for the PEB pre-peeling procedure and the PEB post-peeling procedure. The results are shown in Tables 4 and 5.

The monomers used in the production examples are shown below.

(Manufacturing Example 1) Synthesis of Doped Polymer 1

206 g of the sodium salt of the monomer 1 was dissolved in 1,000 ml of ion-exchanged water, and while stirring at 80 ° C, 1.14 g of an ammonium persulfate oxidizing agent solution previously dissolved in 10 ml of water was added dropwise over 20 minutes, and the solution was stirred. 2 hours.

To the thus obtained solution containing sodium polystyrene sulfonate, 1,000 ml of diluted sulfuric acid of 10% by mass and 10,000 ml of ion-exchanged water were added, and about 10,000 of the solution containing polystyrenesulfonic acid was removed by ultrafiltration. The solution was ml, 10,000 ml of ion-exchanged water was added to the remaining solution, and about 10,000 ml of the solution was removed by ultrafiltration. Repeat the above ultrafiltration operation Do it 3 times.

Further, about 10,000 ml of ion-exchanged water was added to the obtained filtrate, and about 10,000 ml of the solution was removed by ultrafiltration. Repeat this ultrafiltration operation 3 times.

The water in the resulting solution was removed under reduced pressure to give a colorless solid polystyrenesulfonic acid.

In addition, the ultrafiltration conditions are as follows (the same applies to other examples).

‧Molecular weight cut-off of ultrafiltration membrane: 30K

‧ cross flow

‧ Feed liquid flow: 3,000ml / min

‧ Film partial pressure: 0.12Pa

This polymer compound is (doped polymer 1).

(Production Example 2) Synthesis of Doped Polymer 2

37.5 g of methanol stirred under nitrogen atmosphere at 64 ° C, 112.5 g of methanol was dissolved in 4 hours, 37.5 g of monomer 2 and 12.5 g of lithium salt of monomer 1 and 2,2'-azo double were dissolved. A solution of (isobutyric acid) dimethyl ester 3.04 g. Enter The mixture was stirred at 64 ° C for 4 hours. After cooling to room temperature, it was dripped while vigorously stirring 1,000 g of ethyl acetate. The resulting solid was collected by filtration and dried under vacuum at 50 ° C for 15 hours to yield 47.1 g of a white polymer.

The obtained white polymer was dissolved in 424 g of methanol, and the lithium salt was converted into a sulfonic acid group using an ion exchange resin. The obtained polymer was subjected to ¹⁹ F, ¹ H-NMR, and GPC measurement, and the results of the analysis were as follows:

Copolymerization composition ratio (mole ratio) monomer 1: monomer 2 = 1:1

Weight average molecular weight (Mw) = 39,000

Molecular weight distribution (Mw/Mn)=1.81

This polymer compound is (doped polymer 2).

(Production Example 3) Synthesis of Polyaniline-based Conductive Polymer Composite Using Doped Polymer 1

27.5 g of 2-methoxyaniline and 41.1 g of the solution of the doped polymer 1 obtained in Production Example 1 dissolved in 1,000 mL of ultrapure water were mixed at 25 °C.

The mixed solution thus obtained was kept at 0 ° C, and 45.9 g of ammonium persulfate dissolved in 200 mL of ultrapure water was gradually added while stirring, and the mixture was stirred and reacted.

The obtained reaction liquid was concentrated, and then added dropwise to 4,000 mL of acetone to obtain a green powder. This green powder was again dispersed in 1,000 mL of ultrapure water, and 4,000 mL of acetone was dropped, and the green powder was purified and recrystallized. This operation was repeated 3 times, and the obtained green powder was redispersed in 2,000 mL of ultrapure water, and about 1,000 mL of water was removed by ultrafiltration. This operation was repeated 10 times, and 4,000 mL of acetone was again dropped to obtain a green powder of a conductive polymer composite.

This conductive polymer composite is (polyaniline composite 1).

(Production Example 4) Synthesis of a polyaniline-based conductive polymer composite using doped polymer 2

27.5 g of 2-methoxyaniline and 61.1 g of the solution of the doped polymer 2 obtained in Production Example 2 dissolved in 1,000 mL of ultrapure water were mixed at 25 °C.

The mixed solution thus obtained was kept at 0 ° C, and 45.8 g of ammonium persulfate dissolved in 200 mL of ultrapure water was gradually added while stirring, and the mixture was stirred and reacted.

The obtained reaction liquid was concentrated, and then added dropwise to 4,000 mL of acetone to obtain a green powder. This green powder was again dispersed in 1,000 mL of ultrapure water, and 4,000 mL of acetone was dropped, and the green powder was purified and recrystallized. This operation was repeated 3 times, and the obtained green powder was redispersed in 2,000 mL. In ultrapure water, about 1,000 mL of water is removed by ultrafiltration. This operation was repeated 10 times, and 4,000 mL of acetone was again dropped to obtain a green powder of a conductive polymer composite.

This conductive polymer composite is (polyaniline composite 2).

(Example 1)

11.5 g of the polyaniline composite obtained in Production Example 3, 354 g of ion-exchanged water, 0.08 mass% of β-Alanine (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.05% by mass of SURFINOL 465 (manufactured by Nissin Chemical Industry Co., Ltd.) were mixed. Thereafter, the mixture was filtered using a UPE filter subjected to a hydrophilic treatment to prepare a conductive polymer composition.

(Example 2)

A conductive polymer composition was prepared in the same manner as in Example 1 except that the β-Alanine (manufactured by Tokyo Chemical Industry Co., Ltd.) used in Example 1 was changed to 0.04% by mass.

(Example 3)

The 0.08 mass% β-Alanine used in Example 1 was changed to 0.15 mass% L-Carnitine (manufactured by Tokyo Chemical Industry Co., Ltd.), and a conductive polymer composition was prepared in the same manner as in Example 1.

(Example 4)

In addition to the L-Carnitine used in Example 3 (manufactured by Tokyo Chemical Industry Co., Ltd.) The conductive polymer composition was prepared in the same manner except that it was changed to 0.08 mass%.

(Example 5)

11.5 g of the polyaniline composite 2 obtained in Production Example 4, 354 g of ion-exchanged water, 0.08 mass% of β-Alanine (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.05% by mass of SURFINOL 465 (manufactured by Nissin Chemical Industry Co., Ltd.) were mixed. Thereafter, the mixture was filtered using a UPE filter subjected to a hydrophilic treatment to prepare a conductive polymer composition.

(Example 6)

A conductive polymer composition was prepared in the same manner as in Example 5 except that the β-Alanine (manufactured by Tokyo Chemical Industry Co., Ltd.) used in Example 5 was changed to 0.04% by mass.

(Example 7)

In the same manner as in Example 5 except that 0.08 mass% of β-Alanine (manufactured by Tokyo Chemical Industry Co., Ltd.) used in Example 5 was changed to 0.15% by mass of L-Carnitine (manufactured by Tokyo Chemical Industry Co., Ltd.), the conductivity was high as in Example 5. Molecular composition.

(Example 8)

In addition, 0.08 mass% of β-Alanine (manufactured by Tokyo Chemical Industry Co., Ltd.) used in Example 5 was changed to 0.08 mass% of L-Carnitine (Tokyo Chemicals Co., Ltd.) A conductive polymer composition was prepared in the same manner as in Example 5 except for the production.

(Example 9)

The same procedure as in Example 5 was carried out except that 0.08 mass% of β-Alanine (manufactured by Tokyo Chemical Industry Co., Ltd.) used in Example 5 was changed to 0.18 mass% of Dimethylethylammonium propanesulfinate (Wako Pure Chemicals product name: NDSB-195). A conductive polymer composition.

(Embodiment 10)

The same procedure as in Example 5 was carried out except that 0.08 mass% of β-Alanine (manufactured by Tokyo Chemical Industry Co., Ltd.) used in Example 5 was changed to 0.24% by mass of Dimethylbenzylammonium propanesulfinate (Wako Pure Chemicals product name: NDSB-256). A conductive polymer composition.

(Comparative Example 1)

A conductive polymer composition was prepared in the same manner as in Example 1 except that the betaine compound was not used in Example 1.

(Comparative Example 2)

A conductive polymer composition was prepared in the same manner as in Example 5 except that the betaine compound was not used in Example 5.

(Comparative Example 3)

The betaine compound used in Examples 1 to 4 was changed to ammonia water (28% manufactured by Kanto Chemical Co., Ltd.), and a conductive polymer composition was prepared by using the change in pH and surface resistivity of the conductive polymer composition as an index. The amount of ammonia water added was 0.11% by mass.

(Comparative Example 4)

The betaine compound used in Examples 5 to 10 was changed to ammonia water (28% manufactured by Kanto Chemical Co., Ltd.), and a conductive polymer composition was prepared by using the change in pH and surface resistivity of the conductive polymer composition as an index. The amount of ammonia water added was 0.12% by mass.

Tables 1 to 5 show the pore size, film formability, water repellency, resist damage, pH, surface resistance, and the filter pore size of the antistatic film obtained from the conductive polymer composition prepared in each of the examples and the comparative examples. The lithography evaluation of the electron beam plotter.

As shown in Table 1, Examples 1 to 10 which are conductive polymer compositions of the present invention are relative to compositions which are not added with a betaine compound. In Comparative Examples 1 and 2, the pH which is a mitigating index of acidity can be improved, and the surface resistivity of the film is not increased and the film quality is not impaired in Comparative Examples 3 and 4, and it is possible to suppress the acid from causing the resist film. The composition of the influence.

On the other hand, in Comparative Examples 1 and 2, which are compositions in which no betaine compound was added, the antistatic effect was excellent, but the pH was low, and the acid in the composition was easily diffused to the resist to adversely affect the resist pattern. .

Further, in Comparative Examples 3 and 4, it was originally predicted that the pH was improved, but it was found that the conductive polymer composition was deteriorated, discoloration or precipitation occurred, and the surface resistivity also increased, so that it was impossible to form an electron beam resist. The antistatic film functions as a composition applied to the resist.

Further, as shown in Tables 2 to 5, in the evaluation of the lithography using the electron beam, the antistatic film obtained from the conductive polymer composition of the present invention (Examples 1 to 10) was used, and Comparative Example 1 was used. Both of them can control the diachronic change of sensitivity, and the analyticity and shape of the figure are also improved. For the PCD evaluation, the higher the pH, the better the value of the surface resistivity and the storage stability of the resist and the conductive polymer film (antistatic film) can be easily adjusted. On the other hand, Comparative Examples 1 and 2, which are compositions without a betaine compound, are excellent in the above-mentioned antistatic effect, but have a low pH, and in the case of PCD, the resistance is extremely large, and the resist and the conductive polymer are large. There is a problem in the storage stability of the cover of the film. Further, in Comparative Examples 3 and 4, when the amount of the added ammonia water is effective for pH control, the conductive polymer is partially doped and the surface resistivity is increased. Therefore, the function as an antistatic film is obtained. Deterioration occurred.

Further, the present invention is not limited to the above embodiment. Above The embodiment is merely illustrative, and substantially the same configurations as those described in the claims of the present invention and exerting the same effects are included in the technical scope of the present invention.

Claims (13)

A conductive polymer composition comprising a polyaniline-based conductive polymer (A), a polyanion (B), and a betaine compound (C) having a repeating unit represented by the following formula (1). And water or solvent (D); Wherein R ^A1 to R ^A4 each independently represent a linear, branched or cyclic monovalent hydrocarbon group, a hydrogen atom or a halogen atom having a carbon number of 1 to 20; and R ^A1 and R ^A2 , Or R ^A3 and R ^A4 may be bonded to each other to form a ring, and the component (C) is selected from the group consisting of the betaine compounds shown below. A conductive polymer composition comprising a polyaniline-based conductive polymer (A), a polyanion (B), and a betaine compound (C) having a repeating unit represented by the following formula (1). And water or solvent (D); Wherein R ^A1 to R ^A4 each independently represent a linear, branched or cyclic monovalent hydrocarbon group, a hydrogen atom or a halogen atom having a carbon number of 1 to 20; and R ^A1 and R ^A2 , Or R ^A3 and R ^A4 may be bonded to each other to form a ring, and the component (C) is selected from the group consisting of betaine compounds shown below. Or by the following general formula (3): Wherein, R ^B1 ~ R ^B3 each independently represents a substituted heteroatom, or a heteroatom interposed carbon number of 1 to 20 atoms of linear, branched or cyclic monovalent hydrocarbon group, or a hydrogen atom; R ^B1 And R ^B2 , or R ^B1 , R ^B2 and R ^B3 may be bonded to each other to form a ring together with A ⁺ in the formula; A ⁺ is a hetero atom, indicating a monovalent cation; k is an integer of 2-8; L is carbon An atom or a hetero atom, and may have both of these; R ^B4 and R ^B5 independently represent a hydrogen atom, or a linear, branched or cyclic monovalent hydrocarbon group having a carbon number of 1 to 20 interposing a hetero atom; And R ^B4 and R ^B5 may be bonded to each other to form a ring, and the above component (B) includes those represented by the following formula (4): Wherein R ¹ is a hydrogen atom or a methyl group; R ² is a single bond, an ester group, or any one of an ether group and an ester group, or a straight chain, a branch or a ring having a carbon number of 1 to 12; Any one of the hydrocarbon groups; Z is any one of a phenyl group, a naphthyl group, and an ester group; and a is 0 < a ≦ 1.0. The conductive polymer composition of claim 1, wherein the component (B) comprises a compound represented by the following formula (4): Wherein R ¹ is a hydrogen atom or a methyl group; R ² is a single bond, an ester group, or any one of an ether group and an ester group, or a straight chain, a branch or a ring having a carbon number of 1 to 12; Any one of the hydrocarbon groups; Z is any one of a phenyl group, a naphthyl group, and an ester group; and a is 0 < a ≦ 1.0. The conductive polymer composition according to claim 1 or 2, wherein the content of the component (C) is complex with respect to the component (A) and the component (B) 100 parts by mass of the body is from 1 part by mass to 50 parts by mass. The conductive polymer composition of claim 4, wherein the content of the component (C) is from 3 parts by mass to 10 parts by mass based on 100 parts by mass of the composite of the component (A) and the component (B). The conductive polymer composition of claim 1 or 2 further contains a nonionic surfactant. The conductive polymer composition of claim 6, wherein the content of the nonionic surfactant is from 1 part by mass to 50 parts by mass based on 100 parts by mass of the composite of the component (A) and the component (B). . An antistatic film formed of the conductive polymer composition of claim 1 or 2. A cover comprising an antistatic film covering the object to be processed, wherein the antistatic film is formed of the conductive polymer composition of claim 1 or 2. The cover of claim 9, wherein the object to be processed is a substrate having a chemically amplified resist film. The cover of claim 9, wherein the object to be processed is a substrate for irradiating a pattern of an electron beam to obtain a resist pattern. A pattern forming method comprising the steps of: forming an antistatic film using a conductive polymer composition according to claim 1 or 2 on a chemically amplified resist film having a substrate of a chemically amplified resist film; The beam irradiation pattern; and the imaging using an alkaline developing solution to obtain a resist pattern. A substrate having a resist pattern obtained by the pattern forming method of claim 12.