KR101948973B1 - Conductive polymer composition, coated article, patterning process, and substrate - Google Patents
Conductive polymer composition, coated article, patterning process, and substrate Download PDFInfo
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- G03F7/093—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers characterised by antistatic means, e.g. for charge depletion
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Abstract
An object of the present invention is to provide a conductive polymer composition which is excellent in antistatic property, does not adversely affect the resist, has excellent applicability and can be suitably used for lithography using an electron beam or the like.
The conductive polymer composition of the present invention is characterized by containing a polyaniline 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 of a straight, branched or cyclic monovalent hydrocarbon group having 1 to 20 carbon atoms, a hydrogen atom and a halogen atom which may have a hetero atom, and R A1 and R A2 or R A3 and R A4 may be bonded to each other to form a ring)
Description
The present invention relates to a conductive polymer composition comprising a polyaniline-based conductive polymer, a covering product using the same, a pattern forming method, and a substrate. More specifically, the present invention relates to a conductive polymer composition suitably used for electrification prevention of a resist in lithography using ultraviolet rays, electron beams, etc., an article having an antistatic film formed using the composition, a pattern using the conductive polymer composition Forming method, and a substrate obtained by the pattern forming method.
BACKGROUND ART [0002] Conventionally, in the manufacturing process of a semiconductor device such as an IC or an LSI, fine processing is performed by a lithography method using a photoresist. This is a method in which the solubility of the thin film is remarkably changed by causing the crosslinking or decomposition reaction of the thin film to be induced by light irradiation, and the substrate is etched using the resist pattern obtained as a result of the developing treatment with a solvent or the like as a mask. 2. Description of the Related Art In recent years, high-precision microfabrication using light of a short wavelength has been required along with high integration of semiconductor devices. Lithography by electron beam has been developed as a next generation technology from its short wavelength characteristics.
As a problem peculiar to lithography by electron beam, a charging phenomenon (charge up) at the time of exposure can be mentioned. This is a phenomenon in which, when a substrate on which electron beam exposure is performed is covered with an insulating resist film, charges are accumulated on the resist film or charged in the film. This charging causes the trajectory of the incident electron beam to bend, thereby remarkably lowering the accuracy of description. Therefore, an antistatic film to be coated on an electron beam resist has been studied.
In order to alleviate the deterioration in the description accuracy, Patent Document 1 discloses a composition containing a complex containing an aniline-based conductive polymer, a polyacid and H 2 O, and a composite comprising an aniline-based conductive polymer and a polyacid It is specified that an antistatic film capable of peeling and cleaning with H 2 O is formed with sufficient spin-coat film formation at 5 to 10 mass% and a sufficient antistatic effect with a film thickness of 150 nm.
However, when the antistatic film is formed on the chemically amplified resist, the acid generated by the exposure is neutralized by the components in the antistatic film. In the positive type, the resist exposure part is insoluble during development. In the negative type, The resist unexposed portion is partially dissolved at the time of development due to the acid component in the antistatic film and the resist unexposed portion is insoluble at the time of development in the negative type, And fluctuation of sensitivity may be seen in some cases.
Since chemically amplified resists do not have resistance to most organic solvents, many antistatic agents formed on the resist are of the aqueous type. However, since the surface of the chemically amplified resist is hydrophobic and it is necessary to add a surfactant or the like because the water-based antistatic agent is difficult to apply, since the mixing layer is formed on the surface of the resist by the addition of the surfactant, The influence of the acid component in the acid and the antistatic film generated in the resist after the above-described drawing promotes the problem of the resist shape change and sensitivity fluctuation.
Patent Document 2 discloses a conductive composition containing a complex containing an acid group-substituted polyaniline-based conductive polymer and a basic compound, and describes the effect of improving the heat resistance and conductivity under a high-temperature atmosphere, such as application to an electrolytic capacitor have.
In the composition described in Patent Document 1, the presence of an acid derived from a polyacid contained in a composite containing a polyaniline-based conductive polymer and a polyacid has high acidity, so that the antistatic effect is effective, There is an undesirable influence on the lithography as shown.
In the polyaniline-based conductive polymer of Patent Document 2, the polyacid of another molecule as described in Patent Document 1 is not used, and a self-doped polyaniline-based conductive polymer having an acidic substituent group introduced into the aniline monomer forming the conductive polymer , And the aniline-based conductive polymer and the polyacid do not form a complex. Further, the acidic substituent on the aniline monomer exists in a ratio of 1: 1 with the amino group of the aniline. In this regard, in order to adapt to the use and purpose is to change the composition ratio of the aggregate by the amino group and an acidic substituent of the polyaniline-based conductive polymer is difficult, and also to greatly contribute to the mounds acid for the hydrophilic, H 2 O in the art polymer The polymer in the composition tends to re-agglomerate because the ratio of the presence of acid groups not involved in the formation of the complex is limited, and when the composition is applied as an antistatic film on a chemically amplified resist, defects occur.
The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a conductive polymer composition which is excellent in antistatic property, does not adversely affect the resist, is excellent in coating property and can be suitably used for lithography using, The purpose.
In order to solve the above problems,
There is provided a conductive polymer composition comprising a polyaniline 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 of a straight, branched or cyclic monovalent hydrocarbon group having 1 to 20 carbon atoms, a hydrogen atom and a halogen atom which may have a hetero atom, and R A1 and R A2 or R A3 and R A4 may be bonded to each other to form a ring)
Such a conductive polymer composition provides a conductive polymer composition that can be suitably used for lithography using an electron beam or the like because it has excellent antistatic performance, does not adversely affect the resist, and has excellent applicability.
At this time, it is preferable that the component (C) is represented by the following formula (2).
(In the formula, R B1 to R B3 each independently represent a straight, branched or cyclic monovalent hydrocarbon group of 1 to 20 carbon atoms, which may be substituted by a hetero atom, or a hydrogen atom, which may be interrupted by a hetero atom , 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, And L is a carbon atom or a hetero atom, and when k is 2 or more, R B4 and R B5 may be a hydrogen atom or an alkyl group having 1 to 20 carbon atoms straight, branched or cyclic monovalent represents a hydrocarbon group, and R B4 and R B5 may be bonded to each other to form a ring, B - is a monovalent anionic functional group, and the carboxylic acid ion or sulfonic acid ion Represents)
When the conductive polymer composition of the present invention contains a betaine compound represented by the above formula (2) as the component (C), when the antistatic film is formed on the workpiece using the conductive polymer composition, And diffusion of the acid between the antistatic film and the antistatic film can be suppressed, and the influence of the acid can be alleviated.
Also, at this time, it is preferable that the component (C) is represented by the following chemical formula (3).
(Wherein R B1 to R B5 , A + , L and k are as defined above)
When the conductive polymer composition of the present invention contains a betaine compound represented by the above formula (3) as the component (C), when the antistatic film is formed on the workpiece using the conductive polymer composition, The diffusion of the acid between the antistatic film and the antistatic film is further suppressed, and the influence of the acid can be further alleviated.
Also, at this time, it is preferable that the component (B) includes those represented by the following formula (4).
(In the formula, R 1 is a hydrogen atom or a methyl group, and R 2 is a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms which may have a single bond, an ester group, or an ether group or an ester group, A cyclic hydrocarbon group, Z is any one of a phenylene group, a naphthylene group and an ester group, and a is 0 < a? 1.0.
The effect of the present invention can be further improved if the conductive polymer composition of the present invention contains the component represented by the above formula (4) as the component (B).
It is also preferable that the content of the component (C) is 1 part by mass to 50 parts by mass with respect to 100 parts by mass of the composite of the component (A) and the component (B).
When the content of the component (C) is set as such, the acid diffusion from the antistatic film formed by the conductive polymer composition to the resist layer is reduced, and the effect of lithography by acid is maintained while the antistatic effect during electron beam lithography is maintained. And a high-resolution resist pattern can be obtained. Further, from the same effect, it is possible to obtain a resist-processed object having little sensitivity fluctuation even after a time from the film formation to the pattern development.
It is also preferable that the content of the component (C) is 3 parts by mass to 10 parts by mass with respect to 100 parts by mass of the composite of the component (A) and the component (B).
When the content of the component (C) is set to be such as this, acid diffusion from the antistatic film formed by the conductive polymer composition to the resist layer is further reduced, and the antistatic effect during electron beam lithography is maintained, The influence is further reduced, and a resist pattern with higher resolution can be obtained. In addition, from the same effect, a resist processed material with less sensitivity fluctuation can be obtained over time from the film formation to the pattern development.
It is also preferable that the conductive polymer composition further contains a nonionic surfactant.
If this is the case, the wettability to the workpiece such as a substrate can be increased.
It is also preferable that the content of the nonionic surfactant is 1 part by mass to 50 parts by mass with respect to 100 parts by mass of the composite of the component (A) and the component (B).
If this is the case, the wettability to the surface of the resist becomes better, and the antistatic ability is also sufficient.
The conductive polymer composition may be used for forming an antistatic film.
The present invention also provides a coated article on which an antistatic film formed by using the conductive polymer composition is formed on a workpiece.
The antistatic film formed of the conductive polymer composition of the present invention is excellent in antistatic property, and a coated article having high quality can be obtained by covering such antistatic film with various materials to be processed.
Also, at this time, the work piece 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, it is preferable to use a substrate having a chemically amplified resist film, which is difficult to be applied conventionally, as an object to be processed to form an antistatic film formed of the conductive polymer composition of the present invention It is also possible to select.
Also, at this time, the work piece may be a substrate for obtaining a resist pattern by irradiating an electron beam with a pattern.
Since the conductive polymer composition of the present invention can be suitably used for lithography using electron beams or the like, a resist pattern having high sensitivity, high resolution, and good pattern shape can be obtained.
The present invention also provides a method for manufacturing a semiconductor device, comprising the steps of: forming an antistatic film on the resist film of a substrate having a chemically amplified resist film using the conductive polymer composition; irradiating a pattern with an electron beam; The method comprising the steps of:
According to such a pattern formation method, it is possible to prevent a charging phenomenon at the time of exposure, to obtain a resist pattern having high sensitivity, high resolution, and good pattern shape.
Further, the present invention provides a substrate having a resist pattern obtained by the pattern forming method.
With the pattern forming method of the present invention, it is possible to obtain a substrate having a resist pattern having high sensitivity, high resolution, and good pattern shape.
INDUSTRIAL APPLICABILITY As described above, since the conductive polymer composition of the present invention has excellent antistatic property, it can be suitably used for antistatic use. Further, by coating the antistatic film formed using the conductive polymer composition of the present invention on a variety of materials to be processed, a high-quality coated product can be obtained.
In addition, even when the conductive polymer composition of the present invention is applied to a lithography method using a photoresist, since the coating property is excellent without adversely affecting the insolubility of the resist or variation in sensitivity and the like, A resist pattern having high sensitivity, high resolution, and 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.
As described above, the application of the antistatic film to the semiconductor device manufacturing process has been studied in recent years. However, conventional conductive compositions have a problem that the acid contained in the composition adversely affects the resist.
Therefore, the inventors of the present invention have made intensive investigations to solve the above problems. As a result, it has been found that the use of a betaine compound provides an excellent antistatic property, an adverse effect on the resist, an excellent coating property, A conductive polymer composition which can be used can be obtained. Thus, the present invention has been completed.
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 Conductive Polymer]
The conductive polymer composition of the present invention comprises a polyaniline-based conductive polymer represented by the following formula (1) as the component (A).
(Wherein R A1 to R A4 each independently represent any of a straight, branched or cyclic monovalent hydrocarbon group having 1 to 20 carbon atoms, a hydrogen atom and a halogen atom which may have a hetero atom, and R 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 composed of an aniline or derivatives other than para-substituents of aniline. Examples of the polymer having the same function include polypyrrole, polythiophene, polyacetylene, polyphenylene, polyphenylene vinylene, polyacene, polythiophene vinylene, and copolymers thereof.
However, there is a problem in that a high dispersibility to H 2 O, a filtration property of a dispersion, a peelability to an H 2 O or alkaline developer after film formation, a low defectiveness in lithography, an easy polymerization, , A polyaniline-based conductive polymer is selected as the component (A).
The polyaniline-based conductive polymer can attain sufficient conductivity even in the unsubstituted state, but it can exhibit high dispersibility to H 2 O, low coagulation property, filtration ability of the dispersion, improvement in peelability to H 2 O or alkaline developer after film formation, It is more preferable to introduce a substituent for reducing the defect. The substituent may be introduced with a functional group such as a halogen atom, an alkyl group, a carboxyl group, an alkoxy group, a hydroxyl group, or a cyano group.
Specific examples of the aniline monomer used for obtaining the polyaniline-based conductive polymer include aniline, 2-methylaniline, 3-methylaniline, 2-ethylaniline, 3-ethyl aniline, 2-isopropylaniline, 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-ethoxyaniline, 3-ethoxyaniline, 3-isopropoxyaniline, 3-hydroxyaniline, Dimethoxy aniline, 2,5-diethoxy aniline, 2-methoxy-5-methylaniline, 5-tert-butyl-2-methoxy aniline, Chloro-2-methylaniline, 5-chloro-2-methylaniline and the like. Any one of them may be used alone or two kinds Or more It is.
Among them, preferred are 2-methylaniline, 3-methylaniline, 2-ethylaniline, 3-ethylaniline, 2-isopropylaniline, 2-methoxyaniline, 3-methoxyaniline, ethoxy-aniline, 3-isopropoxy aniline, 3-hydroxy-dispersibility and conductivity of the H 2 O when the (co) polymer containing one kind or two kinds selected from aniline is hayeoteul form a complex with a polyanion, Reactivity, and product thermal stability.
[(B) polyanion]
The conductive polymer composition of the present invention comprises 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 and can be obtained by a method of polymerizing a monomer having an anionic group or copolymerizing a monomer having an anionic group and a monomer having no anionic group. These monomers may be used alone or in combination of two or more. Alternatively, it may be obtained by obtaining a polymer having no anionic group, followed by sulfonation with a sulfonating agent such as sulfuric acid, fuming sulfuric acid or sulfamic acid. Further, a polyanion having an anion group content can be obtained by once obtaining a polymer having an anionic group and further sulfonating it.
Examples of the monomer constituting the polyanion used in the present invention include a sulfonic acid group, a sulfonic acid group fluorinated at the? -Position, a phosphoric acid group, or a monomer containing a carboxyl group, and more specifically, -O-SO 3 - H +, -SO 3 - H +, -CH (CF 3) -CF 2 -SO 3 - H +, -CF 2 -SO 3 - H +, -COO - H +, -O-PO 4 - H +, And monomers containing strong acid groups such as -PO 4 - H + . Among these, a polyaniline-based conductive -SO in view of the doping effect of the polymer 3 - H +, -CH (CF 3) -CF 2 -SO 3 - H +, -CF 2 -SO 3 - H +, -COO - H & lt ; + & gt ; is preferred. It is preferable that the anion groups are disposed adjacent to each other or at regular intervals in the main chain of the polyanion.
Examples of the monomer containing a sulfonic acid group include styrene sulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, vinylsulfonic acid, allylsulfonic acid, methallylsulfonic acid, 2- (methacryloxy) ethanesulfonic acid, 4- (methacryloxy) Butane sulfonic acid, isoprenesulfonic acid, 2-acrylamide-2-methylpropanesulfonic acid, 1,1,3,3,3-pentafluoro-2-methacryloyloxypropane-1-sulfonic acid, Methacryloyloxyethanesulfonic acid, 1,1,3,3,3-pentafluoro-2- (4-vinyl-benzoyloxy) -propane-1-sulfonic acid, 1,1-difluoro 2- (4-vinyl-benzoyloxy) -ethanesulfonic acid, benzyltrimethylammonium difluorosulfoacetic acid 2-methacryloyloxyethyl ester, and the like. These monomers may be used alone or in combination of two or more.
Or polystyrene, polymethylstyrene and the like, and then sulfonating the resultant with a sulfonating agent such as sulfuric acid, fuming sulfuric acid or sulfamic acid to obtain a polyanion for use in the present invention.
Further, in Patent Documents 3 and 4, an acid generator of a sulfonium salt of a polymer type in which a sulfonic acid in which the? -Position is fluorinated is generated. The sulfonium salt of the sulfonic acid bound to the polymer main chain fluorinated at the? -Position is a super strong acid with very small diffusion of the sulfonic acid generated by the photolysis of the sulfonium salt, and the above-mentioned polyanion can be obtained by single polymerization or all polymerization of the repeating unit. When the sulfonium salt of the polymer type is in the form of an alkali metal salt, an ammonium salt or an amine salt, an inorganic acid or an organic acid such as sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid or perchloric acid may be added in advance or a solution .
Examples of the monomer containing a carboxyl group include ethylenically unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, 4-vinylbenzoic acid and crotonic acid; Ethylenically unsaturated polycarboxylic acids such as maleic acid, fumaric acid and itaconic acid, and acid anhydrides thereof; And partial esters of ethylenically unsaturated polycarboxylic acids such as methyl maleate, methyl itaconate and the like. These monomers may be used singly or in combination of two or more, and it is more preferable to use them in combination with the sulfonic acid monomer from the viewpoint of the doping effect on the polyaniline-based conductive polymer.
Examples of the monomer containing a phosphoric acid group include 3-chloro-2-acid phosphoxypropyl (meth) acrylate, acid phosphoxypolyoxyethylene glycol mono (meth) acrylate, mono (2-hydroxyethyl acrylate) Mono (2-hydroxypropylmethacrylate) acid phosphate, mono (2-hydroxypropylmethacrylate) acid phosphate, mono (2-hydroxypropylmethacrylate) acidphosphate, mono (3-hydroxypropylmethacrylate) acid phosphate, diphenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate and the like can be given . These monomers may be used singly or in combination of two or more, and they are preferably used in combination with the sulfonic acid monomers in view of the doping effect on the polyaniline-based conductive polymer.
As the other monomer which does not contain an anionic group copolymerizable with the anionic group-containing monomer, known compounds can be used without any limitation. For example, conjugated diene monomers such as 1,3-butadiene, isoprene, 2-chloro-1,3-butadiene and 2-methyl-1,3-butadiene; Aromatic vinyl monomers such as styrene,? -Methylstyrene, and p-methylstyrene; Ethylenically unsaturated carboxylic acid alkyl ester monomers such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate; Ethylenically unsaturated carboxylic acid amide monomers such as acrylamide, methacrylamide, N, N-dimethyl acrylamide and N-methylol acrylamide; Ethylenically unsaturated carboxylic acid hydroxyalkyl ester monomers such as (meth) acrylic acid hydroxyalkyl and glycerin di (meth) acrylate; Carboxylic acid vinyl ester monomers such as vinyl acetate; (Meth) acrylonitrile, N-vinylpyrrolidone, (meth) acryloylmorpholine, cyclohexylmaleimide, isopropylmaleimide, and (meth) acrylate glycidyl.
The above monomers can be polymerized by using, for example, an initiator to obtain a polyanion used in the present invention.
Also, sulfonation of polyether ketone (specification of European Patent Application Publication No. 0041780 (A1)), sulfonation of polyether ether ketone (Japanese Patent Laid-Open Publication No. 2008-108535), sulfonation of polyether sulfone (Japanese Patent Application Laid-Open No. 10-309449), sulfonation of polyphenylene, polyfluorene, polyvinylcarbazole (Japanese Patent Publication No. 2010-514161), sulfonation of polyphenylene oxide, polyphenylene sulfide The polyanion used in the present invention can be obtained.
Among the above polyanions, polyisoprene sulfonic acid, a copolymer containing polyisoprene sulfonic acid, a copolymer containing polysulfoethyl methacrylate, polysulfoethyl methacrylate, poly (4-sulfobutyl methacrylate ), A copolymer comprising poly (4-sulfobutyl methacrylate), a copolymer comprising polymethallyloxybenzenesulfonic acid, polymethallyloxybenzenesulfonic acid, a copolymer comprising polystyrenesulfonic acid and polystyrenesulfonic acid, a poly , 1,3,3,3-pentafluoro-2-methacryloyloxypropane-1-sulfonic acid, poly 1,1,3,3,3-pentafluoro-2- methacryloyloxypropane- Copolymers comprising 1-sulfonic acid, copolymers comprising poly 1,1-difluoro-2-methacryloyloxyethanesulfonic acid, copolymers comprising poly 1,1,3,3,3-pentafluoro-2- (4-vinyl-benzoyloxy) -propane-1-sulfonic acid, copolymers containing poly 1,1-difluoro Methacryloyloxyethyl ester, polydifluorosulfoacetic acid 2-methacryloyloxyethyl ester, is preferably used, as the copolymer, including 2- (4-vinyl-benzoyloxy) -ethanesulfonic acid.
Among them, polystyrene sulfonic acid, poly 1,1,3,3,3-pentafluoro-2-methacryloyloxypropane-1-sulfonic acid, poly 1,1-difluoro-2- methacryloyloxyethane Sulfonic acid, copolymers containing poly 1,1,3,3,3-pentafluoro-2- (4-vinyl-benzoyloxy) -propane-1-sulfonic acid, copolymers containing poly 1,1-di A copolymer comprising fluoro-2- (4-vinyl-benzoyloxy) -ethanesulfonic acid, polydifluorosulfoacetic acid 2-methacryloyloxyethyl ester, polysulfoethyl methacrylate, poly Butyl methacrylate) is more preferable.
As the component (B), those represented by the following formula (4) can also be suitably used.
(In the formula, R 1 is a hydrogen atom or a methyl group, and R 2 is a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms which may have a single bond, an ester group, or an ether group or an ester group, A cyclic hydrocarbon group, Z is any one of a phenylene group, a naphthylene group and an ester group, and a is 0 < a? 1.0.
It is preferable that the repeating unit represented by the formula (4) includes at least one selected from a1 to a4 represented by the following formulas (4-1) to (4-4).
(Of formula, R 1 is the same as above, a1, a2, a3 and a4 are each 0≤a1≤1.0, 0≤a2≤1.0, 0≤a3≤1.0, 0≤a4≤1.0, also 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 in terms of solvent solubility and conductivity. The molecular weight of the polyanion is preferably from 5,000 to 1,000,000. If the lower limit is more than the lower limit, the polyanion tends to be a homogeneous solution, and if the upper limit is not more than the upper limit, the conductivity becomes better.
In the conductive polymer composition according to the present invention, the polyanion is coordinated with the polyaniline-based conductive polymer to form a composite of the polyaniline-based conductive polymer and the polyanion.
(Method for producing a composite of a polyaniline-based conductive polymer and a polyanion)
The composite of the polyaniline-based conductive polymer and the polyanion can be obtained by, for example, adding a monomer as a raw material of the polyaniline-based conductive polymer to an aqueous solution of a polyanion or a water / organic solvent mixture solution of a polyanion, adding an oxidant, . When the polyanion is in the form of an alkali metal salt, ammonium salt or amine salt, it is preferable 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 use an acidic exchange resin to make the solution acid form.
Examples of the oxidizing agent and the oxidizing catalyst include peroxo persulfates such as ammonium peroxodisulfate, sodium peroxodisulfate and potassium peroxodisulfate, transition metal compounds such as ferric chloride, ferric sulfate and cupric chloride, Metal oxides such as cesium oxide, peroxides such as hydrogen peroxide and ozone, organic peroxides such as benzoyl peroxide, oxygen and the like can be used.
As the reaction solvent used in the oxidation polymerization, water or a mixed solvent of water and a solvent can be used. The solvent used herein is preferably a solvent capable of dissolving or dispersing the polyanion or polyaniline-based conductive polymer which can be mixed with water and which will be described later. Polar solvents such as N-methyl-2-pyrrolidone, N, N'-dimethylformamide, N, N'-dimethylacetamide, dimethylsulfoxide and hexamethylphosphoric triamide, alcohols such as methanol, ethanol, Butanol and the like; alcohols such as ethylene glycol, propylene glycol, dipropylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, D-glucose, D-glucitol, isoprene glycol, , Polyvalent aliphatic alcohols such as 5-pentanediol, 1,6-hexanediol, 1,9-nonanediol and neopentyl glycol, carbonate compounds such as ethylene carbonate and propylene carbonate, Cyclic ether compounds such as ethylene glycol monoalkyl ether, ethylene glycol monoalkyl ether, propylene glycol dialkyl ether, polyethylene glycol dialkyl ether, polypropylene glycol dialkyl ether And heterocyclic compounds such as 3-methyl-2-oxazolidinone, and nitrile compounds such as acetonitrile, glutaronitrile, methoxyacetonitrile, propionitrile, benzonitrile, and the like. These solvents may be used alone or as a mixture of two or more kinds. The mixing ratio of these water-miscible solvents to water is preferably 50 mass% or less based on the total amount of the reaction solvent.
The composite of the polyaniline-based conductive polymer and the polyanion thus obtained may be used by atomization using a homogenizer or a ball mill, if necessary.
It is preferable to use a mixed dispersing machine capable of imparting a high shearing force to atomization. Examples of the mixed dispersing machine include a homogenizer, a high-pressure homogenizer, and a bead mill, among which a high-pressure homogenizer is preferable.
Specific examples of the high-pressure homogenizer include trade name Nano-Mizer manufactured by Yoshida Kikai Kogyo Co., microfluidizer manufactured by Paurex Co., and Altimizer manufactured by Suginomachine.
Examples of the dispersion treatment using the high-pressure homogenizer include a treatment for causing the composite solution before the dispersion treatment to be opposed at a high pressure, a treatment for passing the composite solution at high pressure through an orifice or a slit, and the like.
The impurities may be removed by a method such as filtration, ultrafiltration or dialysis before or after atomization, and purification may be performed using a cation exchange resin, an anion exchange resin, a chelate resin or the like.
The total content of the polyaniline 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 mass% or more, sufficient conductivity is obtained. When the total content is 5.0 mass% or less, a uniform conductive film can be easily obtained.
When the pH of the polyaniline 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, indicating strong acidity. However, when the antistatic film is coated with various materials 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. If the pH is in the range of 4 or more and the pH is in the range of 8 or less, the acid corrosion and the acid diffusion to the adjacent layer are suppressed, and if the cover is a resist, the resist becomes less susceptible to damage and the pattern after development becomes better.
The content of the polyanion is preferably such that the anion group in the polyanion is in the range of 0.1 to 10 moles, more preferably in the range of 1 to 7 moles per mole of the polyaniline-based conductive polymer. When the anion group in the polyanion is 0.1 mole or more, the doping effect on the polyaniline-based conductive polymer is high, and sufficient conductivity can be ensured. When the anion group in the polyanion is 10 moles or less, the content of the polyaniline-based conductive polymer is also appropriate, and sufficient conductivity is obtained.
[(C) Betaine compound]
The conductive polymer composition of the present invention includes a betaine compound as the component (C).
In the present invention, any of known betaine compounds may be used.
The betaine compound may be used alone or in combination of two or more.
The betaine compound used in the present invention is preferably represented by the following formula (2).
(In the formula, R B1 to R B3 each independently represent a straight, branched or cyclic monovalent hydrocarbon group of 1 to 20 carbon atoms, which may be substituted by a hetero atom, or a hydrogen atom, which may be interrupted by a hetero atom , 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, And L is a carbon atom or a hetero atom, and when k is 2 or more, R B4 and R B5 may be a hydrogen atom or an alkyl group having 1 to 20 carbon atoms straight, branched or cyclic monovalent represents a hydrocarbon group, and R B4 and R B5 may be bonded to each other to form a ring, B - is a monovalent anionic functional group, and the carboxylic acid ion or sulfonic acid ion Represents)
In the formula (2), A + is a heteroatom and represents a monovalent cation. Examples of A + include sulfonium ions and ammonium ions.
B - is a monovalent anionic functional group, and represents a carboxylic acid ion or a sulfonic acid ion. B - forms an intramolecular salt with A + present in the same molecule or forms a salt with A + of an adjacent molecule between two molecules.
The component (C) is more preferably represented by the following formula (3).
(Wherein R B1 to R B5 , A + , L and k are as defined above)
Among the betaine compounds represented by the above formula (2), the following structures can be specifically exemplified as structures having a sulfonate ion.
Specific examples of the structure of the betaine compound represented by the above formula (3) include the following.
The content of the betaine compound is preferably 1 part by mass to 50 parts by mass, more preferably 3 parts by mass to 10 parts by mass, relative to 100 parts by mass of the composite of the polyaniline conductive polymer and the polyanion. When the content of the betaine compound is set as such, the acid diffusion from the antistatic film formed by the conductive polymer composition of the present invention to the resist layer is reduced, and the antistatic effect during electron beam lithography is maintained, The effect is reduced, and a high-resolution resist pattern can be obtained. Further, from the same effect, it is possible to obtain a resist-processed object having little sensitivity fluctuation even after a time from the film formation to the pattern development.
(Surfactants)
In the present invention, a surfactant may be added in order to increase wettability with respect to a workpiece such as a substrate. Preferable examples of the surfactant include nonionic surfactants. Specific examples thereof include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene carboxylic acid esters, sorbitan esters, polyoxyethylene sorbitan esters, and acetylene glycols.
The content of the nonionic surfactant is preferably 1 part by mass to 50 parts by mass, more preferably 2 parts by mass to 20 parts by mass, per 100 parts by mass of the composite of the polyaniline conductive polymer and the polyanion. If the lower limit is more than the lower limit, the wettability with respect to the resist surface becomes better, and if it is lower than the upper limit, the antistatic performance becomes sufficient.
In order to obtain the conductive polymer composition of the present invention, for example, a complex of a polyaniline conductive polymer and a polyanion, a solvent, a surfactant and the like are mixed, a betaine compound is added, and a high pressure homogenizer is applied And further by filtration through UPE filter.
An antistatic film can be formed by applying the conductive polymer composition thus obtained to an object to be processed such as a substrate. Examples of the application method of the conductive polymer composition include coating with a bar coater, spin coating, dipping, comma coating, spray coating, roll coating, and gravure printing. After the application, an antistatic film is formed by a heat treatment with a hot air circulation path, a hot plate or the like.
Examples of the material to be processed include glass substrates, quartz substrates, photomask blank substrates, resin substrates, silicon wafers, gallium arsenide wafers, and compound semiconductor wafers such as indium-in wafers.
Examples of the coated article coated with the antistatic film obtained by using the conductive polymer composition of the present invention include a glass substrate on which an antistatic film is formed, a resin film on which an antistatic film is formed, and a resist substrate on which an antistatic film is formed.
Particularly, since the conductive polymer composition of the present invention does not adversely affect the resist, it can be suitably used if the substrate to be processed is a substrate having a chemically amplified resist film, and it can be used for obtaining a resist pattern by pattern- In the case of a substrate, more suitable results can be obtained.
The present invention also relates to a method for manufacturing a semiconductor device, comprising the steps of forming an antistatic film using the conductive polymer composition of the present invention on a resist film of a substrate provided with a chemically amplified resist film, a step of irradiating an electron beam with a pattern and an alkaline developer And a step of obtaining a resist pattern.
The pattern forming method may be carried out according to a conventional method except that the conductive polymer composition of the present invention is used. The pattern forming method may be performed after the post-exposure heat treatment is applied, and various other steps such as an etching step, a resist removing step, Of course, it is done.
According to such a pattern formation method, it is possible to prevent a charging phenomenon at the time of exposure, to obtain a resist pattern having high sensitivity, high resolution, and good pattern shape.
Further, the present invention provides a substrate having a resist pattern obtained by the pattern forming method.
Further, although the present invention is designed for use in lithography using an electron beam or the like, it can be suitably used for lithography using ultraviolet rays, antistatic use for films and glass, etc. from its excellent antistatic ability.
<Examples>
Hereinafter, the present invention will be described in more detail with reference to Production Examples, Examples and Comparative Examples, but the present invention is not limited to these Examples.
The measuring method and the evaluation method of each physical property are as follows.
Spin Coater MS-A200 (manufactured by Mikasa Chemical Co., Ltd.) was used for the antistatic film in Examples 1 to 10 and Comparative Examples 1 to 4 and the resist film used as the lower layer by spin coating. The positive type chemically amplified type resist was a positive type chemically amplified electron beam resist (a) manufactured by Shin-Etsu Chemical Co., Ltd. In addition, Shin-Etsu Chemical Co., Ltd. (b) was used for the negative-type chemically amplified electron beam resist.
The positive type chemically amplified type resist (a) and the negative type type chemically amplified type type resist (b) were baked in a precision thermostat at 110 DEG C for 240 seconds to remove the solvent, and the films of Examples 1 to 10 and Comparative Examples 1 to 4 The antistatic film was formed by baking in a precision thermostat at 90 DEG C for 90 seconds to remove the solvent. The resist film thickness and the antistatic film thickness were determined by a spectroscopic ellipsometer VASE (manufactured by WRAM Co., Ltd.) having a variable incident angle.
(Filterability)
After the preparation of the conductive polymer compositions of the following examples and comparative examples, filtration was performed using a UPE filter (manufactured by Entegris) having a pore diameter of 0.5 to 0.050 탆, and the filter was subjected to filtration without causing clogging The pore diameter of the filter was examined. The permeation limit of the UPE filter obtained by filtering the conductive polymer composition in Examples 1 to 10 and Comparative Examples 1 to 4 is shown in Table 1.
(pH measurement)
The pH of the conductive polymer compositions of Examples 1 to 10 and Comparative Examples 1 to 4 was measured using a pH meter D-52 (manufactured by Horiba Seisakusho Co., Ltd.). The results are shown in Table 1.
(Film forming property)
Evaluation was made based on a criterion that a uniform film could be formed and that the refractive index could be measured, but that the film had defects originating from particles or partially distorted. The evaluation results are shown in Table 1.
(Water-splitting property)
10 占 도전 of the conductive polymer composition was dropped onto the film of the resist (a) or the resist (b) obtained by the above film forming method, and the film was heated in a precision thermostat at 90 占 폚 for 90 seconds and then left in air for 2 minutes at room temperature. The formed antistatic film was rinsed with ion-exchanged water in a cleaning bottle. The peeling of the antistatic film within 10 seconds was evaluated as & cir &, the peeling was observed within 10 seconds and within 20 seconds & cir & The evaluation results are shown in Table 1.
(Resist damage)
In the substrate after the evaluation of the water-peelability, it was evaluated that the change in color was not observed in the resist portion of the base on which the antistatic film had been peeled off, that the change in color was visible in some areas, And evaluated. 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 genuine 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 change with time was measured by the influence of the conductive polymer film on the resist film before irradiation. The two-layer film of the resist film and the conductive polymer film formed by the method described below was left in the electron beam drawing apparatus for 7 days, 14 days, and 30 days immediately after the film formation, and then the PEB pre- A resist pattern was obtained by PEB post-peeling process. The variation of the pattern line width in the dynamic sensitivity was determined with respect to the sensitivity when the resist and the conductive polymer film were immediately drawn after film formation.
· PEB exfoliation process evaluation
The positive type chemically amplified resist (a) was spin-coated on a 6-inch silicon wafer using MARK VIII (manufactured by Tokyo Electron Co., Ltd., Coater Developer Cleantrack) and prebaked on a hot plate at 110 캜 for 240 seconds A resist film of 150 nm was prepared. The conductive polymer composition was spin-coated on the resulting wafer with resist using MARK VIII as described above, and baked on a hot plate at 90 DEG C for 90 seconds to prepare a conductive polymer film. The resist pattern was obtained immediately after the application, after 7 days, 14 days and 30 days after the application of the two-layer film of the resist film and the conductive polymer film. First, the wafer immediately after coating was exposed to light using an electron beam exposure apparatus (HL-800D, manufactured by Hitachi High Technologies, Inc., acceleration voltage: 50 keV), and pure water was then flowed for 15 seconds to peel the conductive polymer film, Baked for 240 seconds (PEB: post exposure bake), and developed with a 2.38 mass% aqueous tetramethylammonium hydroxide solution. The prepared patterned wafers were observed with an overhead SEM (scanning electron microscope), and the exposure amount at which the line and space of 400 nm was resolved at 1: 1 was defined as the optimum exposure amount (sensitivity) (μC / cm 2 ). The minimum dimension at the optimum exposure amount was defined as the resolution. A resist pattern was similarly obtained for wafers having 7 days, 14 days, and 30 days after the application, and the exposure amount for resolving the line and space of 400 nm in the wafer immediately after the application was 1: 1 was defined as the optimum exposure amount (sensitivity) / cm < 2 >). The results are shown in Table 2.
· Evaluation of peel-off process after PEB
A wafer having a two-layer film of a resist film and a conductive polymer film was prepared in the same manner as in the PEB pre-peeling process. Pure water was supplied to each of the wafers after 7 days, 14 days, and 30 days after the application for 15 seconds after the electron beam exposure to form a conductive polymer film Baking (PEB: post-exposure bake) at 110 캜 for 240 seconds without performing the peeling process, and development was performed with a 2.38% by mass aqueous solution of tetramethylammonium hydroxide to obtain a resist pattern. The variation of the pattern line width at the optimum exposure amount (sensitivity) (占 폚 / cm 2 ) was measured for the amount of exposure at which the 400 nm line and space was resolved at 1: The results are shown in Table 3.
The positive resist (b) was evaluated in the same manner as the positive resist (a) for the PEB pre-peeling process and the PEB post-peeling process. The results are shown in Tables 4 and 5.
The monomers used in Production Examples are shown below.
(Preparation Example 1) Synthesis of dopant polymer 1
206 g of the sodium salt of Monomer 1 was dissolved in 1,000 ml of ion-exchanged water and 1.14 g of ammonium persulfate oxidant solution dissolved in 10 ml of water was added dropwise over 20 minutes while stirring at 80 DEG C, and the solution was stirred for 2 hours .
1,000 ml and 10,000 ml of ion-exchanged water diluted with 10% by mass of diluted sodium polystyrene sulfonate solution were added, and about 10,000 ml of the polystyrenesulfonic acid-containing solution was removed by ultrafiltration, 10,000 ml of ion-exchanged water was added, and about 10,000 ml of the solution was removed by ultrafiltration. The above ultrafiltration operation was repeated three times.
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. This ultrafiltration operation was repeated three times.
The water in the obtained solution was removed under reduced pressure to obtain a colorless solid polystyrene sulfonic acid.
The ultrafiltration conditions were as follows (as in the other examples).
· Fractional molecular weight of ultrafiltration membrane: 30K
· Cross flow type
· Feed flow rate: 3,000 ml / min
· Membrane partial pressure: 0.12 Pa
This polymer compound is referred to as (dopant polymer 1).
(Production Example 2) Synthesis of dopant polymer 2
A solution obtained by dissolving 37.5 g of Monomer 2, 12.5 g of the lithium salt of Monomer 1 and 3.04 g of dimethyl 2,2'-azobis (isobutyrate) in 112.5 g of methanol was added to 37.5 g of methanol stirred at 64 ° C in a nitrogen atmosphere for 4 hours / RTI > The mixture was stirred at 64 占 폚 for 4 hours. After cooling to room temperature, the solution was added dropwise with vigorous stirring to 1,000 g of ethyl acetate. The resulting solid was filtered off and vacuum dried at 50 < 0 > C for 15 hours to give 47.1 g of a white polymer.
The obtained white polymer was dissolved in 424 g of methanol, and a lithium salt was converted into a sulfo group using an ion exchange resin. The obtained polymer was subjected to 19 F, 1 H-NMR and GPC measurements, and the following analysis results were obtained.
Copolymer composition ratio (molar 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 referred to as (dopant polymer 2).
(Production Example 3) Synthesis of polyaniline conductive polymer complex using dopant polymer 1
27.5 g of 2-methoxyaniline and 41.1 g of the dopant polymer 1 obtained in Preparation Example 1 in 1,000 mL of ultrapure water were mixed at 25 占 폚.
45.9 g of ammonium persulfate dissolved in 200 mL of ultrapure water was added slowly while stirring at 0 째 C, and the mixture was reacted with stirring.
The obtained reaction solution was concentrated and then added dropwise to 4,000 mL of acetone to obtain a green powder. The green powder was again dispersed in 1,000 mL of ultrapure water and added dropwise to 4,000 mL of acetone to refine the green powder. This operation was repeated three times. 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 then added dropwise to 4,000 mL of acetone to obtain a green powder of a conductive polymer composite.
This conductive polymer composite is referred to as (polyaniline composite 1).
(Production Example 4) Synthesis of polyaniline conductive polymer complex using dopant polymer 2
27.5 g of 2-methoxyaniline and 61.1 g of the dopant polymer 2 obtained in Preparation Example 2 in 1,000 mL of ultrapure water were mixed at 25 占 폚.
45.8 g of ammonium persulfate dissolved in 200 mL of ultrapure water was added slowly while stirring at 0 캜, and the mixture was reacted with stirring.
The obtained reaction solution was concentrated and then added dropwise to 4,000 mL of acetone to obtain a green powder. The green powder was again dispersed in 1,000 mL of ultrapure water and added dropwise to 4,000 mL of acetone to refine the green powder. This operation was repeated three times. 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 then added dropwise to 4,000 mL of acetone to obtain a green powder of a conductive polymer composite.
This conductive polymer composite is referred to as (polyaniline composite 2).
(Example 1)
11.5 g of the polyaniline composite 1 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 mass% of SURFINOL 465 (manufactured by Nisshin Chemical Industry Co., Ltd.) were mixed and then filtered using a hydrophilic-treated UPE filter 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? -Alanine used in Example 1 (manufactured by Tokyo Chemical Industry Co., Ltd.) was changed to 0.04 mass%.
(Example 3)
A conductive polymer composition was prepared in the same manner as in Example 1 except that 0.08% by mass of β-alanine used in Example 1 was changed to 0.15% by mass of L-carnitine (manufactured by Tokyo Chemical Industry Co., Ltd.).
(Example 4)
Carnitine (manufactured by TOKYO KASEI KOGYO CO., LTD.) Used in Example 3 was changed to 0.08% by mass, a conductive polymer composition was similarly prepared.
(Example 5)
11.5 g of the polyaniline complex 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 mass% of Surfynol 465 (manufactured by Nisshin Chemical Industries, Ltd.) Thereafter, the mixture was filtered using a hydrophilic-treated UPE filter to prepare a conductive polymer composition.
(Example 6)
A conductive polymer composition was prepared in the same manner as in Example 5 except that? -Alanine (manufactured by Tokyo Chemical Industry Co., Ltd.) used in Example 5 was changed to 0.04% by mass.
(Example 7)
A conductive polymer composition was prepared 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 mass% of L-carnitine (manufactured by Tokyo Chemical Industry Co., Ltd.) .
(Example 8)
A conductive polymer composition was prepared 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 0.08 mass% of L-carnitine (manufactured by Tokyo Chemical Industry Co., Ltd.) .
(Example 9)
Except that 0.08% by mass of? -Alanine (manufactured by Tokyo Chemical Industry Co., Ltd.) used in Example 5 was changed to 0.18% by mass of dimethylethylammonium propane sulphonate (product name: NDSB-195, manufactured by Wako Pure Chemical Industries, Ltd.) Similarly, a conductive polymer composition was prepared.
(Example 10)
Except that 0.08 mass% of β-alanine (manufactured by Tokyo Chemical Industry Co., Ltd.) used in Example 5 was changed to 0.24 mass% of dimethylbenzyl ammonium propane sulfinate (product name: NDSB-256, manufactured by Wako Pure Chemical Industries, Ltd.) Similarly, a conductive polymer composition was prepared.
(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.
(Comparative Example 2)
A conductive polymer composition was prepared in the same manner as in Example 5 except that no betaine compound was used.
(Comparative Example 3)
The conductive polymer composition was prepared by changing the betaine compound used in Examples 1 to 4 to ammonia water (manufactured by Kanto Kagaku KK) to change the pH and the surface resistivity of the conductive polymer composition. Ammonia water was added in an amount of 0.11 mass%.
(Comparative Example 4)
The conductive polymer composition was prepared by changing the betaine compound used in Examples 5 to 10 to ammonia water (manufactured by KANTO CHEMICAL Co., Ltd., 28%) and using the fluctuation of pH and surface resistivity of the conductive polymer composition as an index. Ammonia water was added in an amount of 0.12 mass%.
The results are shown in Tables 1 to 5, and the results are shown in Tables 1 to 5. The results are shown in Tables 1 to 5. The results are shown in Tables 1 to 5, and the results are shown in Tables 1 to 5. .
As shown in Table 1, Examples 1 to 10, which are the conductive polymer compositions of the present invention, can raise the pH as an indicator for alleviating the acidity of Comparative Examples 1 and 2, which are compositions not containing a betaine compound, , A composition capable of suppressing the influence of an acid on the resist film without increasing the surface resistivity of the film or damaging the film quality was obtained.
On the other hand, Comparative Examples 1 and 2, which are compositions not containing a betaine compound, are excellent in antistatic effect, but have low pH, and acid in the composition easily diffuses into the resist, adversely affecting the resist pattern.
In Comparative Examples 3 and 4, improvement of the pH was originally expected, but the phenomenon of deterioration of the conductive polymer composition was confirmed, discoloration or precipitation occurred, and the surface resistivity also increased. Therefore, as an antistatic film for electron beam resist But did not function as a composition to be applied onto a resist.
In addition, as shown in Tables 2 to 5, in the lithography evaluation using an electron beam, those using antistatic films obtained from the conductive polymer composition of the present invention (Examples 1 to 10) The change was controlled, and resolution and pattern shape were improved. As for the PCD evaluation, the higher the pH is, the better the storage stability of the coating of the resist and the conductive polymer film (antistatic film) can be easily adjusted while taking into account the value of the surface resistivity. On the other hand, Comparative Examples 1 and 2, which are compositions without a betaine compound, are excellent in antistatic effect as described above. However, since the pH is low and the fluctuation width is extremely large for PCD, the storage stability of the coating of resist and conductive polymer film There was a problem. With respect to Comparative Examples 3 and 4, when the added amount of ammonia water was added in an amount effective for pH control, deterioration of the function as an antistatic film occurred because the conductive polymer was partially undoped and the surface resistivity increased.
The present invention is not limited to the above-described embodiments. The above embodiment is an example, and any structure that has substantially the same structure as the technical idea described in the claims of the present invention and exhibits similar effects can be included in the technical scope of the present invention.
Claims (14)
(Wherein R A1 to R A4 each independently represent any of a straight, branched or cyclic monovalent hydrocarbon group of 1 to 20 carbon atoms which may have a heteroatom, a hydrogen atom, or a halogen atom, and R A1 and R A2 or R A3 and R A4 may be bonded to each other to form a ring)
Wherein the component (C) is a betaine compound shown below, or
Is selected from a betaine compound represented by the following formula (3).
(In the formula, R B1 to R B3 each independently represent a straight, branched or cyclic monovalent hydrocarbon group of 1 to 20 carbon atoms, which may be substituted by a hetero atom, or a hydrogen atom, which may be interrupted by a hetero atom , R B1 and R B2 or R B1 and R B2 and R B3 may combine with each other to form a ring with A + in the formula, A + is a heteroatom and represents a monovalent cation, R B4 and R B5 each independently represents a hydrogen atom or a straight, branched or cyclic C 1 -C 20 hydrocarbon group, which may be interrupted by a heteroatom, may be the same or different and represents an integer of 1 to 8, L represents a carbon atom or a hetero atom, A branched or cyclic monovalent hydrocarbon group, and R B4 and R B5 may be bonded to each other to form a ring)
(Wherein R 1 is a hydrogen atom or a methyl group and R 2 is a straight, branched or cyclic alkyl group having 1 to 12 carbon atoms which may have a single bond, an ester group, an ether group or an ester group, And Z is any one of a phenylene group, a naphthylene group, and an ester group, and a is 0 < a &le; 1.0.
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| CN112996856B (en) * | 2018-11-15 | 2024-04-09 | 三菱化学株式会社 | Conductive composition and method for producing same, and conductive body and method for producing same |
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| EP2868698B1 (en) | 2012-07-02 | 2016-12-07 | Shin-Etsu Polymer Co. Ltd. | Conductive polymer composition, coated article which is provided with antistatic film obtained from conductive polymer composition, and pattern forming method using conductive polymer composition |
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