WO2011122336A1 - Radiation-sensitive resin composition and pattern forming method - Google Patents

Radiation-sensitive resin composition and pattern forming method Download PDF

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WO2011122336A1
WO2011122336A1 PCT/JP2011/056120 JP2011056120W WO2011122336A1 WO 2011122336 A1 WO2011122336 A1 WO 2011122336A1 JP 2011056120 W JP2011056120 W JP 2011056120W WO 2011122336 A1 WO2011122336 A1 WO 2011122336A1
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group
radiation
formula
resin composition
carbon atoms
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PCT/JP2011/056120
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French (fr)
Japanese (ja)
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剛史 若松
稲葉 潤一郎
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Jsr株式会社
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Priority to JP2010079413 priority
Priority to JP2010225259 priority
Priority to JP2010-225277 priority
Priority to JP2010225277 priority
Priority to JP2010-225259 priority
Priority to JP2010233027 priority
Priority to JP2010-233027 priority
Priority to JP2010-237767 priority
Priority to JP2010237767 priority
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Publication of WO2011122336A1 publication Critical patent/WO2011122336A1/en

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    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20Exposure; Apparatus therefor
    • G03F7/2041Exposure; Apparatus therefor in the presence of a fluid, e.g. immersion; using fluid cooling means
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10Esters
    • C08F220/26Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/039Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G03F7/0397Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having an alicyclic moiety in a side chain
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26Processing photosensitive materials; Apparatus therefor
    • G03F7/30Imagewise removal using liquid means
    • G03F7/32Liquid compositions therefor, e.g. developers
    • G03F7/325Non-aqueous compositions

Abstract

Disclosed is a radiation-sensitive resin composition which is suitable for a liquid immersion exposure process for the formation of a resist pattern, and is also suitable for development by an organic solvent. Specifically disclosed is a radiation-sensitive resin composition which is used in a resist pattern forming method wherein development is carried out by an organic solvent (X). The radiation-sensitive resin composition is characterized by containing (A) a polymer, (B) a radiation-sensitive acid generator, and (C) a solvent, and is also characterized in that the polymer (A) contains at least one repeating unit (a2) that is selected from formula (1-1) to formula (1-7).

Description

The radiation-sensitive resin composition and pattern forming method

The present invention, radiation-sensitive resin composition and an organic solvent development pattern forming method using the same. More specifically, an exposure method for performing continuous exposure after without performing such multiple above for exposure of the post-exposure bake and development, used in patterning in particular by double exposure, immersion, such as water, the radiation-sensitive resin composition can be suitably used for liquid immersion lithography process using a medium and a method of forming a resist pattern using the same.

In the field of microfabrication represented by fabrication of integrated circuit devices, in order to achieve a higher degree of integration we have recently been required enabling microfabrication lithography techniques at the following levels 0.10 .mu.m. Finer patterning in the future (e.g., line width fine resist pattern of about 45 nm) is required. As it means for achieving such a fine pattern formation, and short-wavelength (ArF excimer laser (wavelength 193 nm)) of the light source wavelength of the exposure apparatus, the numerical aperture (NA) of the lens or the like to increase is considered . However, the shorter wavelength of the light source, it is necessary to newly expensive exposure apparatus. Further, the increase of the numerical aperture (NA) of the lens, since the resolution and depth of focus have a trade-off relationship, even increasing the resolution depth of focus is lowered.

Recently, as a lithography technique for solving such a problem, the liquid immersion exposure (liquid immersion lithography) method has been reported. However, until progress even 45nm half pitch of an exposure technique using immersion exposure method (hp) have been said to limit, it has been made more technological development for the 32nmhp generations requiring a finer patterning. Recently, 32 nm line by such complicated devices, increases in density requirements, double patterning process (DP), or a half cycle shifted by superimposition of a sparse line pattern or isolated trench pattern such double exposure process (DE) and space (LS) patterning techniques have been proposed (see non-Patent Document 1).

Further, according to the DP or DE, using the positive resist composition, for example, exposing the first LS pattern of 40 nm, a second exposure process as LS patterns is orthogonal to the first LS it is possible to form a fine contact hole of 40nm by performing.

It has also been proposed further development process using organic solvents acid in the developer (see Patent Document 1). The developing process using an organic solvent, the unexposed part is dissolved in an organic solvent, the exposed portions refers to the process of the pattern is formed in an poorly soluble.

Patent No. 3869306

SPIE2006 Vol. 6153 61531K

However, using such a liquid immersion lithography process, and proposes the specific material suitably used for patterning to perform development with an organic solvent is at present not yet been.

The present invention has such has been made in view of the prior problems of the art, and its object is used in patterning to perform development with an organic solvent, suitably used in liquid immersion lithography process it is to provide a capable radiation-sensitive resin composition.

The present inventors have a result of intensive studies to achieve the above object, by containing the predetermined components in the resin component, it found that it is possible to achieve the above object, leading to completion of the present invention It was. That is, the present invention relates to a radiation-sensitive resin composition used in a resist pattern formation method of performing development with an organic solvent (X), and polymer (A), photoacid generator (B), and contains a solvent (C), the polymer (a), characterized in that it comprises at least one repeating unit (a2) selected from the following formulas (1-1) to formula (1-7) a radiation-sensitive resin composition.

Figure JPOXMLDOC01-appb-C000005
(In formula (1-1) ~ (1-7), R 1 is a hydrogen atom, a methyl group or a trifluoromethyl group .R 2 is a hydrogen atom or a substituted or unsubstituted alkyl having 1 to 4 carbon atoms, a group .R 3 is a hydrogen atom or a methoxy group .A is a single bond, a methylene group, a divalent hydrocarbon radical straight or branched having 2 to 10 carbon atoms or an oxygen atom or a sulfur atom, the .B is a divalent linking group .R 5 .R 4 is a single bond or a divalent linking group is an oxygen atom or a methylene group which is a monovalent organic group having a cyclic carbonate structure .p having is an integer of 2 ~ 3, m is 0 or 1, n is 0 or 1. However, when n is 0, a is single bond, and is never a methylene group B.)

The polymer (A) preferably further comprising at least one repeating unit (a3) ​​selected from the following formulas (2-1) to (2-4).

Figure JPOXMLDOC01-appb-C000006

(In the formula (2-1) ~ (2-4), R 6 is a hydrogen atom, a trifluoromethyl group, or an alkyl group having a carbon number of 1 ~ 3 .R 7 are each independently, a hydrogen atom or a hydroxyl group there .R 8 of linear straight chain or branched hydroxyalkyl group in which .L from 1 carbon atoms which may be substituted with an alkyl group having 1 to 5 carbon atoms 5 of 1 to 5 carbon atoms or a branched divalent hydrocarbon radical .M is a group represented by any one of the following formulas (M1) to the formula (M4) .q is an integer of 1-3.)
Figure JPOXMLDOC01-appb-C000007

The polymer (A) preferably further contains a repeating unit (a1) represented by the following formula (3).

Figure JPOXMLDOC01-appb-C000008

(In the formula (3), R 1 represents a hydrogen atom, each a is .R 9 is a methyl group or a trifluoromethyl group independently represents a linear or branched alkyl group having 1 to 4 carbon atoms or 4 carbon atoms, a monovalent alicyclic hydrocarbon group or a derivative thereof to 20. However, any two R 9 are bonded to each other divalent alicyclic hydrocarbon group or a derivative thereof having 4-20 carbon atoms it may form.)

The present invention includes a resist layer formation step of forming a resist layer by coating the radiation-sensitive resin composition on a substrate, an exposure step of performing irradiation through a photomask to the resist layer, an organic solvent (X) in the resist pattern forming method comprising a developing step of developing said radiation-sensitive resin composition comprises a resist pattern forming method which is the radiation-sensitive resin composition.

The exposure step, and a first exposure step and the second exposure step, it is preferable to perform the first exposure step and the second exposure step in succession.

The organic solvent (X) is, ketone solvents, ester solvents, alcohol solvents, amide solvents, be at least one solvent selected from the group consisting of ether solvents and hydrocarbon solvents preferably.

As the photomask, using the mask to form a line-and-space pattern, a pattern formed in the first exposure step, the pattern formed in the second exposure step, the exposure to cross each other it is preferable.

In the pattern forming method using the radiation-sensitive resin composition of the present invention, by exposure, the exposure unit that generated the acid is a polarity change, and thereby can be less soluble in organic solvents (X) , and consequently, it is possible to easily and reliably patterning an organic solvent developer. Here, by the acid-dissociable group in the polymer (A) as a resin component and polarity change are desorbed, means that changes polarity before and after the elimination of the acid-dissociable group.

According to a method of forming a resist pattern using the radiation-sensitive resin composition and the same of the present invention, in patterning by DE, without using the second resist composition such as DP, multiple exposure process of the resist layer it is possible to form a contact hole pattern by, superior to DP in terms of the alignment accuracy and throughput. Further, it is possible to suitably adopted in liquid immersion lithography process.

In the step of the resist pattern forming method according to the present invention, it is a schematic diagram showing in cross section an example of a state after forming a resist layer on a substrate. In the step of the resist pattern forming method according to the present invention, is a schematic diagram of an example of a state is shown from the top to perform the first exposure to the resist layer. In the step of the resist pattern forming method according to the present invention, is a schematic diagram of an example of a state is shown from the top to carry out a second exposure to the resist layer.

Hereinafter will be described an embodiment of the present invention, the present invention is not limited to the following embodiments. Without departing from the scope of the present invention, based on the ordinary knowledge possessed by those skilled in the art, as appropriate alterations to the following embodiments, it is within the scope of the invention that improvements and the like is added.

<Method of forming a resist pattern>
It will be described with reference to the accompanying drawings, an embodiment of a method for forming a resist pattern of the present invention. In the present specification, the term "line pattern", the resist pattern refers to a LS with the line portions and space portions.

(1) resist layer forming process diagram 1 onto the substrate is a schematic diagram showing in cross section an example of a state after forming the resist layer 2 on the substrate 1. As the substrate 1, it is not particularly limited, for example, may be used conventionally known substrate of silicon wafer, such as a wafer coated with aluminum. Further, in order to bring out the potential of the radiation-sensitive resin composition to the maximum, for example, as disclosed in KOKOKU 6-12452 and JP 59-93448 Patent Publication, the substrate used it is also possible to be formed the anti-reflection film of an organic or inorganic above.

Resist layer 2 can be formed by applying a radiation-sensitive resin composition on a substrate. The radiation-sensitive resin composition is a radiation-sensitive resin composition of the present invention described below. Method of applying is not limited in particular, it can be carried out spin coating, cast coating, by an appropriate application method roll coating. Although not particularly limited in thickness of the resist layer 2 formed, usually from 10 ~ 1000 nm, is preferably 10 ~ 500 nm.

Further, after applying the radiation-sensitive resin composition, if necessary, prebaking (hereinafter, also referred to as "PB") may be the solvent evaporated in the coating film by. Heating conditions PB is appropriately selected depending on the composition of the radiation-sensitive resin composition 3 is usually about 30 ~ 200 ° C., preferably from 50 ~ 0.99 ° C..

Furthermore, in order to prevent the influence of basic impurities and the like contained in the environmental atmosphere, for example, as disclosed in JP-A 5-188598 Patent Publication, it is also possible to provide a protective film on the resist layer. Also, possible in order to prevent outflow of the acid generator and the like from the resist layer, for example, as disclosed in JP 2005-352384 Patent Publication, also possible to provide a liquid immersion lithography protective film on the resist layer . Note that these techniques may be used in combination.

(2) As shown in the exposure process diagram 2, using the radiation-sensitive resin composition, through a mask having a predetermined LS pattern in the region of Shoyo after forming the resist layer 2 on the substrate 1, optionally, water, etc. through the immersion liquid, it carried out from above the plan view of the exposure to the exposure unit 3.

As further shown in FIG. 3, it is exposed from above of a plan view with respect to the second exposure portion 4 so as to intersect the first exposure portion 3 continues. It is preferable that the first exposure portion 3 and the second exposure unit 4 perpendicular. By orthogonal, perfectly circular contact hole pattern is easily formed in the unexposed portion 5 surrounded by the exposed portion 3 and the exposure unit 4. Further, the contact hole may be formed in a single exposure by using a mask dot pattern. At the time of exposure, it may be via an immersion liquid such as optionally water or a fluorine-containing inert liquid.

As radiation used for exposure, the radiation-sensitive acid generator contained in the radiation-sensitive resin composition (B) (hereafter, referred to as "acid generator (B)" and also referred to) in accordance with the type of ultraviolet, far ultraviolet, X-rays, is properly selected from the charged particle beam and the like. Among these, preferably deep ultraviolet rays represented by an ArF excimer laser (wavelength 193 nm) or KrF excimer laser (wavelength 248 nm), far ultraviolet rays by ArF excimer laser (wavelength 193 nm) is particularly preferred. Exposure conditions such as the dose are appropriately selected depending on the type of blending composition and additives of the radiation-sensitive resin composition or the like.

Further, a heat treatment after exposure bake (hereinafter, also referred to as "PEB") is preferably performed. By performing PEB, it can smooth progress of the dissociation reaction of the acid-dissociable group or an acid labile group of the radiation-sensitive resin composition. Temperature of PEB is appropriately selected depending on the composition of the radiation-sensitive resin composition, usually from 30 ~ 200 ° C., it is preferably 50 ~ 170 ° C..

(3) performs a development step exposure process development using an organic solvent (X) later to form a contact hole pattern onto a substrate.

Preferable examples of the organic solvent (X), can be used ketone solvents, ester solvents, alcohol solvents, ether solvents, polar solvents such as amide solvents, and hydrocarbon solvents.

Examples of the ketone solvents, 1-octanone, 2-octanone, 2-nonanone, acetone, 4-heptanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methyl cyclohexanone, phenyl acetone, methyl ethyl ketone, and methyl isobutyl ketone and the like.

Examples of the ester solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxy propionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, propyl formate, ethyl lactate, butyl lactate, propyl and the like.

Examples of the alcohol solvents include methyl alcohol, ethyl alcohol, n- propyl alcohol, isopropyl alcohol, n- butyl alcohol, sec- butyl alcohol, tert- butyl alcohol, isobutyl alcohol, n- hexyl alcohol, n- heptyl alcohol, ethylene glycol , like or glycol-based solvent such as triethylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol, propylene glycol, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, glycol monoethyl ether and methoxymethyl butanol It is.

Examples of the ether solvents, in addition to the glycol ether solvents, dioxane, tetrahydrofuran and the like.

Examples of the amide solvents, N- methyl-2-pyrrolidone, N, N- dimethylacetamide, N, N- dimethylformamide and the like.

Examples of the hydrocarbon solvent, toluene, aromatic hydrocarbon solvents such as xylene, pentane, hexane, octane, aliphatic hydrocarbon solvents decane.

Butyl acetate Among these organic solvents (X), isopropyl acetate, amyl acetate, methyl amyl ketone is preferred. The organic solvent (X) may be a mixture of a plurality may be used mixed with a solvent or water other than those described above.

(4) In the rinsing step after the development rinsing step, rinsing solution containing a alkane solvents, ketone solvents, at least one organic solvent selected from ester solvents, alcohol solvents, amide solvents and ether solvents preferably washing with. More preferably, after the development, it is to perform a ketone solvent, an ester solvent, an alcohol solvent, a step of washing with a rinsing solution containing at least one organic solvent selected from amide-based solvents. Even more preferably, after negative development, it is to perform rinsing with a rinse liquid containing an alcohol solvent or an ester solvent. Particularly preferably, after negative development, it is to perform the step of washing with a rinsing solution containing a monohydric alcohol having 6-8 carbon atoms. The monovalent alcohol having 6 to 8 carbon atoms used in the rinsing step after negative development, a linear, branched, include monohydric alcohol which, specifically, 1-hexanol, 1-heptanol, 1-octanol, 2-hexanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol, and the like can be used benzyl alcohol, preferably, 1- hexanol, 2-hexanol, 2-heptanol.

Each component of the rinsing liquid may be a mixture of a plurality may be used mixed with other organic solvents. The water content in the rinsing solution is preferably 10 mass% or less, even more preferably 5 wt% or less, particularly preferably 3 mass% or less. The water content can be obtained good developing characteristics to 10 mass% or less.
The rinsing solution may be further added an appropriate amount of a surfactant.

A resist pattern forming method of the present invention, as shown in FIG. 3, it is preferable that the line part of the resist pattern is formed so as to cross each other. In the intersection to each other, the contact hole pattern can be formed on the substrate by development using an organic solvent (X).

<Radiation-sensitive resin composition>
The radiation-sensitive resin composition, the action of the acid generated from the photoacid generator upon exposure, generate a carboxyl group acid-dissociable group or an acid labile group resides in the composition dissociates, as a result, exposed portion is lowered in solubility in organic solvents (X), the unexposed portion is dissolved by the organic solvent (X), is removed, is capable of forming a pattern. It is particularly suitable for forming a contact hole pattern. The following describes radiation-sensitive resin composition of the present invention.

The radiation-sensitive resin composition contains a polymer including a repeating unit having an acid labile group and (A), acid generator (B), and a solvent (C). Incidentally, referred to herein as "acid labile group" and "acid-dissociable group" is a group released by both acid and not to say special different groups. Having an acid labile group or acid labile group, polymer soluble in an organic solvent (X) is, by a carboxyl group by the action of an acid is the acid labile groups or acid-dissociable group dissociates , it becomes insoluble or hardly soluble polymer in an organic solvent (X).

<Polymer (A)>
Polymer (A), comprising at least one recurring unit (a2) selected from the above-mentioned formula (1-1) to formula (1-7).
(I) the repeating unit (a2)
Repeating unit (a2) is obtained by polymerizing a monomer represented by the corresponding formula (1a-1) ~ formula (1a-7).

Figure JPOXMLDOC01-appb-C000009

In Formula (1a-1) to Formula (1a-7), R 1 , R 2, R 3, R 4, R 5, A, B, p, m, n in Formula (1-1) to Formula ( 1-7) as synonymous.

The substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, represented as R 2 in the above formula (1-1), include methyl group, ethyl group, propyl group, butyl group or their structural isomers, the It is.

Examples of the divalent linking group having an oxygen atom or a sulfur atom represented by A in the above formula (1-2) and formula (1-3), -Ra-O-Rb -, - Ra-CO-Rb- , it may be mentioned divalent groups represented by -Ra-COO-Rb-, or -Ra-S-Rb-. Ra and Rb each independently represent a single bond or a hydrocarbon group having 1 to 10 carbon atoms. As the divalent linking group include groups represented by the following formula (A-1) ~ formula (A-6).

Figure JPOXMLDOC01-appb-C000010

In the above formula (A-1) ~ formula (A-6), R a1 and R b1 are independently of one another hydrogen atom, a methyl group, an ethyl group or a propyl group. Also, q, r represents an integer of 0 to 5 independently of each other. However, q and r are not 0 at the same time during one of the linking groups.

Examples of the divalent linking group represented as R 4 in the above formula (1-7), a hydrocarbon group having 1 to 10 carbon atoms, -Rc-O-Rd -, - Rc-CO-Rd -, - Rc -COO-Rd -, in the divalent groups represented can be exemplified. Rc and Rd each independently represents a hydrocarbon group having 1 to 10 carbon atoms. Incidentally, Rc and Rd are the backbone side oxygen atom, or may be bonded to either R 5.

The R 5 in the formula (1-7), the following formula (1-7a), can be exemplified groups represented by (1-7b).

Figure JPOXMLDOC01-appb-C000011

In the formula (1-7a), n 1 represents an integer of 0-2. In the formula (1-7b), n 2 ~ n 5 each independently represents an integer of 0-2. In the formula (1-7a) and the formula (1-7b), "*" represents a bond that binds to R 4 in the formula (1-7). Further, the group represented by the formula (1-7a) and the formula (1-7b) may have a substituent.

Preferred groups represented by the formula (1-7a) or formula (1-7b), may be mentioned those represented by the following formula (1-7aa) or (1-7bb).

Figure JPOXMLDOC01-appb-C000012

In formula (1-7Aa) and formula (1-7Bb), "*" represents a bond that binds to R 4 in the general formula (1-7).

Specific examples of the repeating unit (1-7) include those represented by the following formula. Incidentally, R 1 in the formula (1-7-1) - (1-7-22) has the same meaning as R 1 in the formula (1-7).

Figure JPOXMLDOC01-appb-C000013

Figure JPOXMLDOC01-appb-C000014

Figure JPOXMLDOC01-appb-C000015

Monomer giving the repeating unit represented by the formula (1-7), for example, Tetrahedron Letters, Vol. 27, No. 32 p. 3741 (1986), Organic Letters, Vol. 4, No. 15 p. 2561 (2002) described the like, it can be synthesized by a conventionally known method.

As a monomer giving the repeating unit (a2), illustrate preferred monomers below.

Figure JPOXMLDOC01-appb-C000016

Figure JPOXMLDOC01-appb-C000017

Polymer (A) may also comprise only one kind of repeating unit (a2), may contain two or more. The content of the repeating unit (a2), relative to the total 100 mol% of the repeating units contained in the polymer (A), usually not more than 80 mol%, preferably 20 ~ 80 mol%, more preferably 30 ~ it is 70mol%. When the content of the repeating unit (a2) is within this range, it is particularly effective from the viewpoint of suppression and significant pattern top loss effect of suppressing scum after photolithography.

(Ii) the repeating unit (a3)
Polymer (A) preferably contains at least one repeating unit (a3) ​​selected from the above-mentioned formula (2-1) to (2-4). Polymer (A), that contains a repeating unit (a3), it is possible to improve the etching resistance of the exposed portion.

The alkyl groups of formula (2-1) to 1 carbon atoms represented as R 6 in (2-4) 1-3, methyl group, ethyl group, a propyl group.

Examples of the linear or branched hydroxyalkyl group having 1 to 5 carbon atoms, represented as R 8, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group or hydrogen structural isomers thereof, atom been substituted with a hydroxyl group.

Examples of the linear or branched hydrocarbon group of alkyl-1 carbon atoms which may be substituted with group 5 having 1 to 5 carbon atoms, represented as L, a methylene group, an ethylene group, a propylene group, butylene group and the like.

Further, M represents a group represented by any of the above formulas (M1) ~ formula (M4). Further, the formula (M1), the orientation of the binding of the formula (M2) does not matter. For example, in the formula (M1), even if the oxygen atoms bonded to bridgehead position of the adamantane, -CH 2 - may be bonded to.

q represents an integer of 1 to 3, and more preferably q = 1.

As the polymerizable monomer giving the repeating unit (a3), it may be mentioned compounds represented by the following formula (2-a) ~ (2-t). In the present invention, as the polymerizable monomer giving the repeating unit (a3), but is not limited thereto.

Figure JPOXMLDOC01-appb-C000018

Figure JPOXMLDOC01-appb-C000019

Figure JPOXMLDOC01-appb-C000020

Figure JPOXMLDOC01-appb-C000021

Polymer (A) may also comprise only one kind of repeating unit (a3), may contain two or more. The content of the repeating unit (a3), relative to the total 100 mol% of the repeating units contained in the polymer (A), usually not more than 60 mol%, preferably 60 ~ 5 mol%, more preferably 50 ~ it is a 5mol%. When the content of the repeating unit (a3) ​​is within this range, it improved etching resistance of the exposed area.

(Iii) repeating unit (a1)
Polymer (A) preferably contains a repeating unit (a1) containing an acid labile group represented by the above formula (3).

Examples of the linear or branched alkyl group having 1 to 4 carbon atoms, represented as R 9 in the formula (3), a methyl group, an ethyl group, n- propyl group, i- propyl, n- butyl group , 2-methylpropyl group, 1-methylpropyl group, and a t- butyl group and the like are.

The monovalent alicyclic hydrocarbon group or a derivative thereof having 4 to 20 carbon atoms, norbornane, tricyclodecane, tetracyclododecane, adamantane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane and the like cyclo alicyclic consisting ring groups derived from alkanes, such as; the group consisting of alicyclic ring, for example, a methyl group, an ethyl group, n- propyl group, i- propyl, n- butyl group, 2- methylpropyl group, 1-methylpropyl group, t- butyl group having 1 to 4 linear carbon atoms, and substituted groups, and the like, branched or cyclic alkyl group.

Moreover, as either two divalent alicyclic hydrocarbon group or a derivative thereof wherein R 9 is 4 to 20 carbon atoms which is formed by bonding to each other, norbornane, tricyclodecane, tetracyclododecane, adamantane, cyclopentane, consisting alicyclic ring derived from cyclohexane group; a group consisting of alicyclic ring, for example, a methyl group, an ethyl group, n- propyl group, i- propyl, n- butyl group, 2-methylpropyl group, substituted with a 1-methylpropyl group, a linear or branched alkyl group having 1 to 4 carbon atoms a t- butyl group and the like or an alicyclic hydrocarbon group having 3 to 10 carbon atoms, group, and the like.

In the formula (3), suitable examples of the group represented by -C (R 9) 3, t-butyl group, 1-n-(1-ethyl-1-methyl) propyl group, 1-n-( 1,1-dimethyl) propyl group, 1-n-(1,1-dimethyl) butyl group, 1-n-(1,1-dimethyl) pentyl group, 1- (1,1-diethyl) propyl group, 1 -n-(1,1-diethyl) butyl group, 1-n-(1,1-diethyl) having no alicyclic ring groups such as pentyl, 1- (1-methyl) cyclopentyl group, 1- ( 1-ethyl) cyclopentyl group, 1- (1-n-propyl) cyclopentyl group, 1- (1-i-propyl) cyclopentyl group, 1- (1-methyl) cyclohexyl group, 1- (1-ethyl) cyclohexyl group , 1- (1-n- propyl) cyclohexyl group, 1- (1-i- Propyl) cyclohexyl group, 1- (1-methyl-1- (2-norbornyl)) ethyl group, 1- (1-methyl-1- (2-tetra tricyclodecanyl)) ethyl group, 1- (1-methyl 1- (1-adamantyl)) ethyl group, 2- (2-methyl) norbornyl group, 2- (2-ethyl) norbornyl group, 2- (2-n-propyl) norbornyl group, 2- (2-i - propyl) norbornyl group, 2- (2-methyl) tetracyclododecanyl group, 2- (2-ethyl) tetracyclododecanyl group, 2- (2-n-propyl) tetracyclododecanyl group, 2- ( 2-i-propyl) tetracyclododecanyl group, 2-methyl-2-adamantyl group, 2-ethyl-2-adamantyl group, 2-propyl-2-like adamantyl group alicyclic group having a ring; these alicyclic A group having a ring, for example, a methyl group, an ethyl group, n- propyl group, i- propyl, n- butyl, 2-methylpropyl group, 1-methylpropyl group, 1 carbon atoms a t- butyl group and the like linear or branched alkyl group having 1-10, cyclopentyl group, cyclohexyl group, and a group obtained by substituting a cyclic alkyl group having 4-20 carbon atoms, such as cyclooctyl group.

Among the monomers providing the repeating unit (a1) be (meth) acrylic acid 2-methyl-adamantyl-2-yl ester, (meth) 2-ethyl-adamantyl-2-yl ester of acrylic acid, (meth) acrylic acid -2 - methylbicyclo [2.2.1] hept-2-yl ester, (meth) acrylic acid-2-ethylbicyclo [2.2.1] hept-2-yl ester, (meth) acrylic acid 1- (bicyclo [2.2.1] hept-2-yl) -1-methylethyl ester, (meth) 1- acrylate (adamantan-1-yl) -1-methylethyl ester, (meth) acrylic acid 1-methyl - 1-cyclopentyl ester, (meth) acrylic acid 1-ethyl-1-cyclopentyl ester, (meth) acrylic acid 1-methyl-1-cyclohexyl ester, (main ) Acrylic acid 1-ethyl-1-cyclohexyl ester, and the like are particularly preferable.

As the monomer giving the repeating unit (a1), illustrate preferred monomers below.

Figure JPOXMLDOC01-appb-C000022

Polymer (A) may also comprise only one kind of repeating unit (a1), may contain two or more. The content of the repeating unit (a1), relative to the total 100 mol% of the repeating units contained in the polymer (A), preferably 20 ~ 90 mol%, more preferably 20 ~ 80 mol%, more preferably it is 20 ~ 70mol%. When the content of the repeating unit (a1) is within this range, the water repellency ensured after coating, is particularly effective from the viewpoint of compatibility between increase in the contact angle with respect to the developing solution after PEB.

(IV) other recurring units polymer (A), the repeating unit (a1), repeating units (a2) and the repeating units (a3) ​​other than the repeating unit (hereinafter, also referred to as "other recurring units") one it may include more.

The other repeating units, for example, repeating units represented by formula (4) (hereinafter, also referred to as "repeating unit (a4)"), the repeating unit represented by the formula (5) (hereinafter, "repeating unit ( a5) "and also referred to), the formula (b-2-1) represented by the repeating unit (b-2-1), the repeating unit represented by the formula (b-2-2) (b-2-2) there are other than these other recurring units (a6) and the like.

Figure JPOXMLDOC01-appb-C000023

In the formula (4), R 10 is a hydrogen atom, a methyl group or a trifluoromethyl group. Y is a single bond or a divalent organic group having 1 to 3 carbon atoms. W is a substituted or unsubstituted polycyclic alicyclic hydrocarbon group having 7 to 20 carbon atoms. However, the polycyclic if the alicyclic hydrocarbon group has a substituent, the substituent is a linear or branched alkyl groups, cyclic alkyl group having 4 to 20 carbon atoms having 1 to 10 carbon atoms, hydroxyl group, a cyano group, a hydroxyalkyl group having 1 to 10 carbon atoms, a carboxyl group or oxo group.

Figure JPOXMLDOC01-appb-C000024

In the formula (5), R 11 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a trifluoromethyl group or a hydroxymethyl group. R 12 is a divalent organic group.

The substituted or unsubstituted polycyclic alicyclic hydrocarbon group of the formula (4), 7 to 20 carbon atoms, represented as W, for example, represented by the following formula, bicyclo [2.2.1] heptane (4a), bicyclo [2.2.2] octane (4b), tricyclo [5.2.1.0 2, 6] decane (4c), tetracyclo [6.2.1.1 3, 6. 0 2,7] dodecane (4d), tricyclo [3.3.1.1 3, 7] hydrocarbon group derived from a cycloalkane such as decane (4e) can be mentioned.

Figure JPOXMLDOC01-appb-C000025

If the hydrocarbon group derived from the cycloalkane has a substituent, examples of the substituent include methyl group, ethyl group, n- propyl group, i- propyl, n- butyl group, 2- methylpropyl group, 1-methylpropyl group, a linear or branched alkyl group having 1 to 10 carbon atoms a t- butyl group and the like, cyclopentyl group, cyclohexyl group, cyclic C 4 -C 20, such as cyclooctyl group and the like of the alkyl group. Incidentally, the substituent is not limited to these alkyl groups, a hydroxyl group, a cyano group, a hydroxyalkyl group having 1 to 10 carbon atoms, a carboxyl group, may be an oxo group.

In the formula (5), the alkyl group having 1 to 4 carbon atoms, represented as R 11, for example, a methyl group, an ethyl group, n- propyl group, i- propyl, n- butyl, 2-methylpropyl group, 1-methylpropyl group, a t- butyl group and the like can be mentioned.

In the formula (5), the divalent organic group represented by R 12, a divalent hydrocarbon group. Incidentally, alkylene glycol group may be an alkylene ester group. As divalent organic group include a methylene group, an ethylene group, 1,3-propylene group or 1,2-propylene group, a propylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, undecamethylene group, dodecamethylene group, tridecamethylene group, tetradecamethylene group, pentadecamethylene group, hexamethylene, decamethylene group, heptadecamethylene group, octadecamethylene group , nonadecamethylene group, Ikosaren group, 1-methyl-1,3-propylene group, 2-methyl-1,3-propylene group, 2-methyl-1,2-propylene group, 1-methyl-1,4 butylene, 2-methyl-1,4-butylene group, an ethylidene group, a propylidene group, a chain and 2-propylidene group Hydrocarbon group; cyclobutylene groups such as 1,3-cyclobutylene group, 1,3-cyclopentylene cyclopentylene group such as alkylene group, 1,4-cyclohexylene-cyclohexylene group such as a group, 1,5-cyclo monocyclic hydrocarbon ring groups such as a cycloalkylene group having 3 to 10 carbon cyclooctylene group such as octylene group; 1,4-norbornylene group or 2,5-norbornylene norbornylene group such as, 1, It is mentioned 5-adamantylene group or 2,6-adamantylene 2-4 bicyclic bridged cyclic hydrocarbon ring groups such as hydrocarbon cyclic group having 4 to 30 carbon atoms, such as adamantylene group such group it can. Of these, the hydrocarbon group containing a 2,5-norbornylene group, 1,2-ethylene group, a propylene group are preferable.

In the case where R 12 contains a divalent aliphatic hydrocarbon ring group, bis trifluoromethyl - hydroxy - methyl group (-C (CF 3) 2 OH ), 2 divalent aliphatic cyclic hydrocarbon it is preferable to dispose an alkylene group having 1 to 4 carbon atoms as a spacer between the hydrogen group.

Figure JPOXMLDOC01-appb-C000026

The repeating unit (a6), carboxyl group-containing esters having a bridged hydrocarbon skeleton of an unsaturated carboxylic acid; no bridged hydrocarbon skeleton (meth) acrylate; unsaturated carboxylic acids carboxyl group-containing esters having no bridged hydrocarbon skeleton; polymerization of multifunctional monomers and the like having no bridged hydrocarbon skeleton; polyfunctional monomer having a bridged hydrocarbon skeleton sex unsaturated bond is a unit such as that cleaved. Among these, repeating units are preferably polymerizable unsaturated bond bridged hydrocarbon having a skeleton (meth) acrylic acid esters have been cleaved. Incidentally, polymer (A), the repeating unit (a4) ~ (a6), may also comprise only one kind of (b-2-1) or (b-2-2), comprising two or more it may be the one.

As monomers which provide the other recurring units, illustrate preferred monomers below.

Figure JPOXMLDOC01-appb-C000027

Figure JPOXMLDOC01-appb-C000028

[Process for the preparation of the polymer (A)]
Polymer (A), for example, using a polymerizable unsaturated monomer that produces the repeating units described above, hydroperoxides such, dialkyl peroxide, a diacyl peroxide, a radical polymerization initiator such as an azo compound and, the presence of a chain transfer agent, if necessary, can be prepared by polymerizing in a suitable solvent.

The solvent used for the polymerization, for example, n- pentane, n- hexane, n- heptane, n- octane, n- nonane, alkanes such as n- decane; cyclohexane, cycloheptane, cyclooctane, decalin, norbornane cycloalkanes and the like; benzene, toluene, xylene, ethylbenzene, aromatic hydrocarbons such as cumene; chlorobutane, bromohexane, dichloroethane, hexamethylene dibromide, halogenated hydrocarbons such as chlorobenzene; ethyl acetate, n- butyl acetate i- butyl, saturated carboxylic acid esters such as methyl propionate; acetone, 2-butanone, 4-methyl-2-pentanone, ketones such as 2-heptanone; tetrahydrofuran, dimethoxyethane, etc. diethoxyethane there is ether, and the like. These solvents may be used singly or may be used in combination of two or more.

[Physical properties of the polymer (A)]
The weight average molecular weight in terms of polystyrene by gel permeation chromatography (GPC) of the polymer (A) (hereinafter, also referred to as "Mw") but is not particularly limited, respectively, is 1,000 to 100,000 it is preferred, more preferably from 1,000 to 30,000, more preferably 1,000 to 20,000. If the Mw is less than 1,000, there is a possibility that the heat resistance of the resist layer is lowered. On the other hand, if it is more than 100,000, there may decrease developability of the alkali developing unit.

Furthermore, the Mw of each polymer, the number average molecular weight in terms of polystyrene by gel permeation chromatography of the polymer (GPC) (hereinafter, also referred to as "Mn") ratio of (Mw / Mn) of each normally 1 to 5 is preferably 1-3.

The polymer (A) may contain low molecular weight components derived from the monomers used in preparing. The content of the low molecular weight component, for each polymer 100 wt% (solid basis), preferably less 0.1 wt%, more preferably not more than 0.07 wt%, more preferably 0.05 mass% or less. If the content of the low molecular weight component is 0.1 wt% or less, it is possible to reduce the amount of elution into the immersion liquid such as water in contact at the immersion exposure. Also, less foreign matter in the resist during the time of the resist storage occurs also less likely to coating unevenness occurs at the time of resist coating, the occurrence of defects during resist pattern formation can be sufficiently suppressed.

In the present specification, the term "low molecular weight component", Mw good 500 following components, specifically, mention may be made of monomers, dimers, trimers, oligomers. Low molecular weight components, for example, washing with water, liquid-liquid chemical purification method and the like extraction, these chemical purification method and ultrafiltration, can be removed by a combination of a physical purification method such as centrifugation. Further, analysis can be performed by high performance liquid chromatography (HPLC).

Further, the polymer (A), halogen, it is preferred that less impurities such as metal. By reducing the impurity, the sensitivity of the formed resist layer, the resolution, process stability, because it is possible to further improve the pattern profile and the like.

The purification method of the polymer (A), for example, washing with water, liquid-liquid chemical purification method and the like extraction, these chemical purification method and ultrafiltration, the combination of a physical purification method such as centrifugation is there.

<Acid generator (B)>
As the acid generator (B), an onium salt compound, halogen-containing compounds, diazoketone compounds, sulfone compounds, sulfonate compounds, and the like. Acid generator (B) is preferably a compound represented by the following formula (6).

Figure JPOXMLDOC01-appb-C000029

In the above formula (6), R 13 is a hydrogen atom, a fluorine atom, a hydroxyl group, a linear or branched alkyl group having 1 to 10 carbon atoms, straight-chain or branched alkoxy group having 1 to 10 carbon atoms , or represents a straight-chain or branched alkoxycarbonyl group having 2 to 11 carbon atoms. Further, R 14 is a linear or branched alkyl group having 1 to 10 carbon atoms, straight-chain or branched alkoxy group having 1 to 10 carbon atoms, or C 1 -C 10 straight, branched It represents a Jo or cyclic alkanesulfonyl group. Furthermore, R 15 are independently of each other, represent a linear or branched alkyl group, a phenyl group or a naphthyl group, having 1 to 10 carbon atoms. Two R 15 may form a divalent group having 2 to 10 carbon atoms containing sulfur cations bonded to each other. However, the phenyl group, a naphthyl group, and a divalent group having 2 to 10 carbon atoms may have a substituent. k represents an integer of 0 to 2, r represents an integer of 0 to 10 (preferably an integer of 0 to 2). X - represents an anion represented by the following formula (7-1) to (7-4).

Figure JPOXMLDOC01-appb-C000030

In the formula (7-1) and (7-2), R 16 represents a fluorine atom or substituted 1 carbon atoms which may be 1-12 hydrocarbon group. In the formula (7-1), t is an integer of 1-10. In the formula (7-3) and (7-4), R 17 are independently of each other, represent a linear or branched alkyl group of carbon number of 1 to 10 substituted by a fluorine atom. Further, two R 17 may form a divalent organic group of carbon number of 2 to 10 substituted by a fluorine atom bonded to one another. However, a divalent organic group having 2 to 10 carbon atoms which is substituted with a fluorine atom may have a substituent other than fluorine atoms.

Acid generator (B) may contain an acid generator represented by the above formula (6), or the exemplified acid generator alone, it may contain two kinds or more.

The proportion of the acid generator (B), with respect to the radiation-sensitive resin composition 100% by weight, 20% by weight or less, preferably 1 to 15 mass%. Also, when using the other acid generator, the use proportion, the acid generator relative to (B) 100 wt%, usually 80 wt% or less, preferably 60 wt% or less.

<Solvent (C)>
As the solvent (C), for example, 2-butanone, 2-pentanone, 3-methyl-2-butanone, 2-hexanone, 4-methyl-2-pentanone, 3-methyl-2-pentanone, 3,3-dimethyl 2-butanone, 2-heptanone, 2-straight or branched ketones such as octanone; cyclopentanone, 3-methyl cyclopentanone, cyclohexanone, 2-methylcyclohexanone, 2,6-dimethyl cyclohexanone, isophorone cyclic ketones and the like; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono -n- propyl ether acetate, propylene glycol monomethyl -i- propyl ether acetate, propylene glycol mono -n- Buchiruete Acetate, propylene glycol monobutyl -i- ether acetate, propylene glycol monobutyl -sec- butyl ether acetate, propylene glycol monoalkyl ether acetates such as propylene glycol monobutyl -t- butyl ether acetate; 2-hydroxypropionic acid methyl, 2-hydroxypropionic acid ethyl, 2-hydroxy propionic acid n- propyl, 2-hydroxypropionic acid i- propyl, 2-hydroxy propionic acid n- butyl, 2-hydroxypropionic acid i- butyl, 2-hydroxypropionic acid sec- butyl, 2-hydroxy 2-hydroxypropionic acid alkyl such as propionic acid t- butyl; methyl 3-methoxypropionate, 3-methoxy ethyl propionate, 3-ethoxy Methyl propionic acid, other 3-alkoxy propionic acid alkyl such as ethyl 3-ethoxypropionate,

n- propyl alcohol, i- propyl alcohol, n- butyl alcohol, t- butyl alcohol, cyclohexanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono -n- propyl ether, ethylene glycol monobutyl -n- butyl ether , diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol di -n- propyl ether, diethylene glycol di -n- butyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono -n- propyl ether acetate, propylene glycol monomethyl ether , propylene glycol monoethyl Ether, propylene glycol mono -n- propyl ether, toluene, xylene, 2-hydroxy-2-methylpropionic acid ethyl, ethoxyethyl acetate, hydroxyethyl acetate, 2-hydroxy-3-methyl-butyric acid methyl, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, 3-methyl-3-methoxybutyl butyrate, ethyl acetate, n- propyl acetate, n- butyl, methyl acetoacetate, ethyl acetoacetate, methyl pyruvate, ethyl pyruvate, N- methylpyrrolidone, N, N- dimethylformamide, N, N- dimethylacetamide, benzyl ethyl ether, di -n- hexyl ether, diethylene glycol monomethyl ether, diethylene Monoethyl ether, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, and diethyl maleate, .gamma.-butyrolactone, ethylene carbonate and propylene carbonate .

Among these, linear or branched ketones, cyclic ketones, propylene glycol monoalkyl ether acetates, 2-hydroxypropionic acid alkyls, 3-alkoxy propionic acid alkyl ethers, .gamma.-butyrolactone and the like are preferable.

The radiation-sensitive resin composition may contain solvent (C) singly, or may include two or more kinds. The amount of the solvent (C), the total solid content of the radiation-sensitive resin composition is usually an amount of 1 to 50 mass%, an amount that preferably is 1 to 25 mass%.

<Additives>
The radiation-sensitive resin composition, if necessary, refers acid diffusion controller (D), alicyclic additives, surfactants, sensitizers, fluorine atom-containing polymer (hereinafter, also the polymer (F) ) may contain various additives such as.

(I) Acid diffusion controller (D):
Acid diffusion control agent, exposure by controls diffusion in the resist layer of acid generated from the acid generator (B), is a component to suppress undesired chemical reactions in the unexposed area. By containing such an acid diffusion controller, the storage stability of the radiation-sensitive resin composition is improved. Further, with the resolution as a resist is further improved, can be suppressed a change in line width of the resist pattern due to fluctuation of the holding time period from exposure to heat treatment after exposure (PED), extremely excellent composition process stability things can be obtained.

As the acid diffusion controller, for example, amine compounds, amide group-containing compounds, urea compounds, nitrogen-containing heterocyclic compounds.

(Amine compound)
Mono (cyclo) alkylamines; di (cyclo) alkyl amines; tri (cyclo) alkylamines; substituted alkyl aniline or derivatives thereof; ethylenediamine, N, N, N ', N'-tetramethylethylenediamine, tetramethylenediamine , hexamethylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl, 4,4'-diamino diphenylamine, 2,2-bis (4-aminophenyl) propane, 2- (3-aminophenyl) -2- (4-aminophenyl) propane, 2- (4-aminophenyl) -2- (3-hydroxyphenyl) propane, 2- (4-aminophenyl) -2- ( 4-hydroxyphenyl) propane, 1,4-bis (1- (4-aminophenyl ) -1-methylethyl) benzene, 1,3-bis (1- (4-aminophenyl) -1-methylethyl) benzene, bis (2-dimethylaminoethyl) ether, bis (2-diethylaminoethyl) ether, 1- (2-hydroxyethyl) -2-imidazolidinone, 2-quinoxalinium linoleic, N, N, N ', N'-tetrakis (2-hydroxypropyl) ethylenediamine, N, N, N', N '' , N '' - there is pentamethyldiethylenetriamine, and the like.

(Amide group-containing compound)
Preferable examples of the amide group-containing compounds, other N-t-butoxycarbonyl-pyrrolidine N-t-butoxycarbonyl group-containing amino compounds such as, formamide, N- methylformamide, N, N- dimethylformamide, acetamide, N- methylacetamide, N, N- dimethylacetamide, propionamide, benzamide, pyrrolidone, N- methylpyrrolidone, N- acetyl-1-adamantyl amines, isocyanuric acid tris (2-hydroxyethyl) and the like.

(Urea compound)
Preferable examples of the urea compounds, urea, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, tri -n- butyl there is a thiourea and the like.

(Nitrogen-containing heterocyclic compounds)
Preferable examples of the nitrogen-containing heterocyclic compound, imidazoles, pyridines, other piperazines, pyrazine, pyrazole, pyridazine, quinoxaline, purine, pyrrolidine, piperidine, piperidineethanol, 3-piperidino-1,2-propanediol, morpholine, 4-methylmorpholine, 1- (4-morpholinyl) ethanol, 4-acetyl morpholine, 3- (N-morpholino) -1,2-propanediol, 1,4-dimethylpiperazine, 1,4-diazabicyclo [2 .2.2] there is octane and the like.

Further, as an acid diffusion controller, in addition to the acid diffusion control agent described above, and sensitized by exposure, a base may also be used photodegradable base that generates.

(Photodegradable base)
As an example of a photodegradable base, there is an onium salt compound loses decomposing acid diffusion controllability upon exposure. Specific examples of such onium salt compound, mention may be made of or sulfonium salt compound represented by the formula (8), the iodonium salt compound represented by the formula (9).

Figure JPOXMLDOC01-appb-C000031

R 18 ~ R 20 in the formula (8), and formula (9) R 21 ~ R 22 in independently of one another are a hydrogen atom, an alkyl group, an alkoxyl group, a hydroxyl group or a halogen atom. Further, in the equation (8) and (9), Z - is, OH -, R 23 -COO - , R 23 -SO 3 - ( where, R 23 is an alkyl group, an aryl group or alkaryl group, represented), or an anion represented by the formula (10).

Figure JPOXMLDOC01-appb-C000032

In the formula (10), R 24 is a linear or branched alkyl group having a substituted or unsubstituted C 1 -C 12 fluorine atoms or a straight or branched alkoxy group having 1 to 12 carbon atoms, the stands, n represents an integer of 0-2. Incidentally, these acid diffusion control agents may be used singly or may be used as a mixture of two or more.

The content of the acid diffusion control agent, relative to the polymer (A) 100 parts by mass of, preferably 0.001 to 15 parts by mass, more preferably from 0.01 to 10 parts by weight, 0. and more preferably 05 to 5 parts by weight. When the content is 15 parts by mass, there is a case where the sensitivity of the resist is lowered. On the other hand, is less than 0.001 part by weight, depending on the process conditions, there is a case where the pattern shape or dimensional accuracy as a resist may decrease.

(Ii) alicyclic additives:
Alicyclic additive is a component that dry etching resistance, the pattern shape, a further effect of improving the adhesion to a substrate, and the like. The alicyclic additives, for example, 1-adamantane carboxylic acid, 2-adamantanone, butyl t-1-adamantane carboxylic acid, 1-adamantane carboxylic acid t- butoxycarbonyl, 1- adamantane carboxylic acid α- butyrolactone , 1,3-adamantane dicarboxylic di -t- butyl, 1-adamantane acetic acid t- butyl, 1-adamantane acetic acid t- butoxycarbonyl methyl, 1,3-adamantane diacetic acid di -t- butyl, 2,5-dimethyl adamantane derivatives such as 2,5-di (adamantylcarbonyloxy) hexane; deoxycholate t- butyl, deoxycholic acid t- butoxycarbonyl methyl, deoxycholic acid 2-ethoxyethyl, deoxycholic acid 2-cyclohexyloxyethyl , deoxycholate - oxocyclohexyl deoxycholate tetrahydropyranyl, deoxycholic acid esters such as deoxycholic mevalonolactone ester; lithocholic acid t- butyl, lithocholic acid t- butoxycarbonyl, 2- ethoxyethyl lithocholic acid, lithocholic acid 2 - cyclohexyloxy ethyl, lithocholic acid 3-oxo-cyclohexyl, lithocholic acid tetrahydropyranyl, lithocholic acid esters such as lithocholic mevalonolactone ester; 3- (2-hydroxy-2,2-bis (trifluoromethyl) ethyl) tetracyclo [6.2.1.1 3,6. 0 2,7] there is dodecane. Incidentally, These alicyclic additives may be used singly or may be used in combination of two or more.

(Iii) Surfactant:
Surfactant is a component having an effect of improving applicability, striation, developability, and the like.

As the surfactant, such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene n- octyl phenyl ether, polyoxyethylene n- nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol other nonionic surfactants such as distearate, in the following trade names, (Shin-Etsu Chemical Co., Ltd.) KP341, Polyflow No. 75, No. 95 (or more, Kyoeisha Chemical Co., Ltd.), F-Top EF301, the EF303, the EF352 (manufactured by Tochem Products Co., Ltd.), Megafac F171, the F173 (manufactured by Dainippon Ink and Chemicals, Inc.), Fluorad FC430, the FC431 (manufactured by Sumitomo 3M), Asahi guard AG710, Surflon S-382, the SC-101, the SC-102, the SC-103, the SC-104, the SC-105, the SC-106 ( above, there is manufactured by Asahi Glass Co., Ltd.), and the like. These surfactants may be used singly or may be used in combination of two or more.

(Iv) a sensitizer:
Sensitizer absorbs radiation energy and transmit the energy to the acid generator (B), thereby shows the effect of increasing the amount of acid generated, the radiation-sensitive resin composition only over the It has the effect of improving the sensitivity.

The sensitizer, carbazoles, acetophenones, benzophenones, naphthalenes, phenols, biacetyl, eosine, rose bengal, pyrenes, anthracenes, a phenothiazine, and the like. Incidentally, these sensitizers may be used singly or may be used in combination of two or more.

(V) a fluorine atom-containing polymer (F)
The radiation-sensitive resin composition, by containing a fluorine atom-containing polymer (F), in forming the resist film, the oil repellency characteristics of the fluorine-containing polymer in the film, the distribution of the resist film tends to unevenly distributed near the surface, can be an acid generator and the acid diffusion controller during immersion exposure, etc. are prevented from being eluted into the liquid immersion medium.

The fluorine-containing polymer (F), as long as it has fluorine atoms, but are not limited to, [A] a polymer from a fluorine atom content (mass%) is higher, it is preferable. By high fluorine atom content than [A] polymer, the degree of uneven distribution of the above becomes higher, properties such as water repellency and suppressing elution of the resulting resist film is improved.

(Vi) other additives:
The radiation-sensitive resin composition may contain additives other than the additives described above (hereinafter, referred to as "other additives") it may contain. Other additives, low molecular weight alkali solubility controllers containing having an alkali-soluble resin, an acid dissociable protecting group, a halation inhibitor, a preservation stabilizer, a defoaming agent and the like. Further, by containing a dye or pigment, a latent image in the exposed area visible, it is possible to reduce the influence of halation during exposure. Further, by incorporating an adhesion aid, it is possible to improve the adhesion to the substrate.

The radiation-sensitive resin composition, that after the respective components described above are dissolved in a solvent (C), prepared as a coating solution by filtration, for example, pore diameter of about 0.2μm filter, coated on a substrate it can.

It will be specifically described with reference to the present invention examples, but the present invention should not be construed as being limited to these examples. In Examples, "parts" and "%" in the comparative examples are by weight unless otherwise specified. Also shows the measurement method of various physical values ​​and evaluation methods of various properties in the following.

[Weight average molecular weight (Mw) and number-average molecular weight (Mn)]
Tosoh Corporation GPC column (G2000HXL2 present, G3000HXL1 present, G4000HXL1 present) using a flow rate: 1.0 mL / min, elution solvent: tetrahydrofuran, column temperature: analysis condition 40 ° C., by gel permeation chromatography (GPC), It was measured monodisperse polystyrene as a standard.

[13 C-NMR Analysis
13 C-NMR analysis of the polymer was measured using a JEOL Ltd. "JNM-EX270".

[Pattern evaluation]
Single patterning (hereinafter, also referred to as SE) and an evaluation board after a contact hole pattern formation formed in DE, scanning electron microscope (Hitachi Instruments Inc., CG-4000) was used to observe the resist pattern loss or if there is adhesion of the insoluble matter was evaluated as "B (bad)", resolved to the hole filling scum without bottom, and the case where the contact hole patterns are formed was evaluated as "a (good)".

[Etching rate Evaluation]
The evaluation substrate after forming a contact hole pattern using a simple etching apparatus was observed, 60% or less of those in the film thickness residual film ratio after etching initially evaluated as "B (bad)", 60 was evaluated as "a (good)," the case better than%.

Hereinafter, describes a process for the preparation of the polymer (A). Incidentally, showing polymer monomer used to prepare the (A) (M-1) ~ monomer the (M-26) below. In the monomer (M-1) ~ monomer (M-26), a monomer giving the repeating unit (a1) is a monomer (M-1) ~ monomer (M-5), monomer monomer giving the repeating unit (a2) (M-7) ~ a monomer (M-13), monomer monomer giving the repeating unit (a3) ​​(M-14) ~ a monomer (M-23), a monomer giving the other repeating units is a monomer (M-6) and the monomer (M-24) - monomer (M-26) .

Figure JPOXMLDOC01-appb-C000033

Figure JPOXMLDOC01-appb-C000034

Figure JPOXMLDOC01-appb-C000035

[Polymerization Example 1] Preparation monomer of the polymer (A-1) (M-11) 50mol%, the monomer (M-3) 15mol%, the monomer (M-2) 35mol%, and a polymerization initiator agent (dimethyl-2,2'-azobis isobutyrate (MAIB)) were prepared monomer solution in methyl ethyl ketone 100 g. The total amount of the monomer at the time of charging was prepared to 50g. Incidentally, mol% of each monomer represents mol% for monomeric total amount, the proportion of the polymerization initiator, the total amount of monomer and a polymerization initiator, and a 5 mol%. Methyl ethyl ketone 50g was added to a three neck flask 500mL equipped with a thermometer and dropping funnel and nitrogen was purged for 30 minutes. Thereafter, while stirring the flask with a magnetic stirrer, it was heated to a 80 ° C.. Then, a monomer solution was prepared in a flask, it was added dropwise over 3 hours using a dropping funnel. After completion of the dropwise addition was aged 3 hours, the polymer solution was obtained by cooling to a 30 ° C. or less. Thereafter, the polymer solution was mixed was poured into methanol 1000 g. Then, it was carried out suction filtration. Thereafter, the powder was collected, re-poured into methanol of 200 g, washed, and filtered. It performs the cleaning again, and the recovered powder was dried under reduced pressure at 60 ° C.. The resulting polymer polymer and (A-1). The polymer (A-1), Mw is 6,200, Mw / Mn is 1.5, 13 C-NMR analysis revealed that the content of the repeating unit derived from the monomer ( M-3) / was a copolymer of (M-2) / ((M-11) = 14.6 / 35.9 / 49.5 (mol%).

Polymerization Examples 2 to 21] Polymer (A-2) ~ (A-16), the polymer (F-1) ~ (F-5) of Preparation Polymer (A-2) ~ (A-16) and for the polymer (F-1) ~ (F-5), except for using a monomer type and charged amounts shown in Table 1 were prepared in the same manner as polymerization example 1. Incidentally, in Table 2, the content of the repeating units derived from each monomer by 13 C-NMR of the polymer, describing the Mw, and Mw / Mn.

Figure JPOXMLDOC01-appb-T000036

Figure JPOXMLDOC01-appb-T000037

Polymers prepared as the polymer (A) of Example 1 radiation-sensitive resin composition (A-1) 100 parts of an acid generator as an acid generator (B) (B-1) (triphenylsulfonium nonafluoro -n- butane sulfonate) 7.5 parts of the nitrogen-containing compound (D) as an acid diffusion controller (D-1) (N-t- butoxycarbonyl pyrrolidine) 0.94 parts of the polymer as the polymer (F) ( F-2) 5 parts, and the solvent (C) as the solvent (C-1) (propylene glycol monomethyl ether acetate) 1287 parts of the solvent (C-2) (cyclohexanone) 551 parts was added, and mixing the components to obtain a homogeneous solution. Thereafter, by filtration through a membrane filter having a pore size of 200 nm, to prepare a radiation-sensitive resin composition.

[Examples 2 to 16 and Comparative Example 1
Except that the formulation described in Table 3 were prepared in to the radiation-sensitive resin composition as in Example 1.

Figure JPOXMLDOC01-appb-T000038

Incidentally, it referred acid generator used in Table 1, solvent, and the type of acid diffusion controller below.

Acid generator (B-1): triphenylsulfonium nonafluoro -n- butane sulfonate solvent (C-1): Propylene glycol monomethyl ether acetate solvent (C-2): cyclohexanone Acid diffusion controller (D-1): N -t- butoxycarbonylpyrrolidine

On Example 17 Formation of resist pattern 12-inch silicon wafer, bottom anti-reflective film (trade name "ARC66", Brewer Science Ltd.) was used trade name "Lithius Pro-i" (manufactured by Tokyo Electron Limited) was spin-coated with, PB (205 ℃, 60 seconds) to form a coating having a thickness of 77nm by performing. Trade name "CLEAN TRACK ACT 12" radiation-sensitive composition prepared in Example 1 using the (1) was spin-coated, PB (130 ° C., 60 seconds), and then cooled (23 ° C., 30 sec) to form a resist layer having a thickness 90nm by. Using the formed resist layer, the following DE pattern to form a SE pattern were each evaluated.

[DE pattern]
ArF immersion exposure apparatus (trade name "S610C", NIKON Co., Ltd.) was used, NA: 1.30, in the optical conditions of the Dipole, a mask for pattern formation of 48nm line / 96nm pitch (48nm1L / 1S) It was exposed to light through. As Thereafter Subsequently perpendicular to the previous exposure, is exposed to light via a mask for pattern formation of 48nm line / 96 nm pitch (48nm1L / 1S). Paddle trade name "Lithius Pro-i" PEB (125 ° C., 60 seconds) on a hot plate of the cooling (23 ° C., 30 seconds) and then, using GP nozzle of the development cup, butyl acetate as a developing solution development (10 sec), and rinsed with 4-methyl-2-pentanol. 2000 rpm, by spin drying at shaking for 15 seconds to obtain an evaluation substrate contact hole pattern 48nm Hall / 96 nm pitch are formed. Evaluation of and the etching rate of DE pattern of the evaluation substrate was "A (good)".

[SE pattern]
Using an ArF immersion exposure apparatus (trade name "S610C", NIKON, Inc.), NA: 1.30, in the optical conditions of the cross-pole, with 48nm dot / 96nm pitch (mask bias is + 15nm, actually on the mask in exposed through a mask for pattern formation of 252nm has become dots / 384 nm pitch). Paddle trade name "Lithius Pro-i" PEB (125 ° C., 60 seconds) on a hot plate of the cooling (23 ° C., 30 seconds) and then, using GP nozzle of the development cup, butyl acetate as a developing solution development (30 sec), and rinsed with 4-methyl-2-pentanol. 2000 rpm, by spin drying at shaking for 15 seconds to obtain an evaluation substrate contact hole pattern 48nm Hall / 96 nm pitch are formed. Evaluation of and the etching rate of the SE pattern of the evaluation substrate was "A (good)".

[Examples 18-32, Comparative Example 2]
Except as described in Table 4 to obtain each evaluation substrate in the same manner as in Example 17. Together evaluation results of the evaluation substrate that were obtained are set forth in Table 4.

Figure JPOXMLDOC01-appb-T000039

As can be seen from Table 4, according to the resist pattern forming method using the radiation-sensitive composition of the present invention, SE, a DE both pattern is "A (good)", etching resistance is also good (A) from, it is possible to form a pattern of greater than wavelength limit. On the other hand, in Comparative Example 2 using the radiation-sensitive composition of Comparative Example 1, SE, evaluation of DP pattern was "B (bad)".

According to the resist pattern forming method using the radiation-sensitive composition of the present invention, since a pattern exceeding a wavelength limit can be satisfactorily and economically formed, radiation-sensitive composition and a pattern forming method of the present invention, can be extremely suitably used in the field of microfabrication represented by fabrication of integrated circuit devices in the future is expected more and more miniaturization progresses.

1 substrate 2 resist layer 3 first exposure portion 4 second exposure portion 5 unexposed portion

Claims (7)

  1. A radiation-sensitive resin composition used in a resist pattern formation method of performing development with an organic solvent (X),
    Containing a polymer (A), photoacid generator (B), and a solvent (C),
    The polymer (A) is a compound represented by the following formula (1-1) or radiation-sensitive resin composition characterized by comprising at least one repeating unit (a2) selected from the following formulas (1-7).
    Figure JPOXMLDOC01-appb-C000001

    (In formula (1-1) ~ (1-7), R 1 is a hydrogen atom, a methyl group or a trifluoromethyl group .R 2 is a hydrogen atom or a substituted or unsubstituted alkyl having 1 to 4 carbon atoms, a group .R 3 is a hydrogen atom or a methoxy group .A is a single bond, a methylene group, a divalent hydrocarbon radical straight or branched having 2 to 10 carbon atoms or an oxygen atom or a sulfur atom, the .B is a divalent linking group .R 5 .R 4 is a single bond or a divalent linking group is an oxygen atom or a methylene group which is a monovalent organic group having a cyclic carbonate structure .p having is an integer of 2 ~ 3, m is 0 or 1, n is 0 or 1. However, when n is 0, a can not single bond and B is a methylene group.)
  2. The polymer (A) is a compound represented by the following formula (2-1) or radiation-sensitive resin composition according to claim 1, further comprising at least one repeating unit (a3) ​​selected from the formula (2-4).
    Figure JPOXMLDOC01-appb-C000002

    (In the formula (2-1) ~ (2-4), R 6 is a hydrogen atom, a trifluoromethyl group, or an alkyl group having a carbon number of 1 ~ 3 .R 7 are each independently, a hydrogen atom or a hydroxyl group there .R 8 of linear straight chain or branched hydroxyalkyl group in which .L from 1 carbon atoms which may be substituted with an alkyl group having 1 to 5 carbon atoms 5 of 1 to 5 carbon atoms or a branched divalent hydrocarbon radical .M is a group represented by any one of the following formulas (M1) to the formula (M4) .q is an integer of 1-3.)
    Figure JPOXMLDOC01-appb-C000003
  3. The polymer (A) is radiation-sensitive resin composition according to claim 1, further comprising a repeating unit (a1) represented by the following formula (3).
    Figure JPOXMLDOC01-appb-C000004

    (In the formula (3), R 1 represents a hydrogen atom, each a is .R 9 is a methyl group or a trifluoromethyl group independently represents a linear or branched alkyl group having 1 to 4 carbon atoms or 4 carbon atoms, a monovalent alicyclic hydrocarbon group or a derivative thereof to 20. However, any two R 9 are bonded to each other divalent alicyclic hydrocarbon group or a derivative thereof having 4-20 carbon atoms it may form.)
  4. A resist layer forming step of forming a resist layer by coating the radiation-sensitive resin composition on a substrate, an exposure step of performing irradiation through a photomask to the resist layer, developing developed with organic solvent (X) in the resist pattern forming method comprising a step, the radiation-sensitive resin composition, a resist pattern forming method is a radiation-sensitive resin composition of claim 1.
  5. The exposure step, and a first exposure step and the second exposure step, a resist pattern forming method according to claim 4 for the first exposure step and the second exposure step in succession.
  6. The organic solvent (X) is, ketone solvents, ester solvents, alcohol solvents, amide solvents, according to claim 4 is at least one solvent selected from the group consisting of ether solvents and hydrocarbon solvents resist pattern forming method.
  7. As the photomask, using the mask to form a line-and-space pattern, a pattern formed in the first exposure step, the pattern formed in the second exposure step, the exposure to cross each other the resist pattern forming method according to claim 5.
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US9523913B2 (en) 2011-05-30 2016-12-20 Fujifilm Corporation Pattern forming method, actinic ray-sensitive or radiation-sensitive resin composition, resist film, method for manufacturing electronic device, and electronic device
JP2013100472A (en) * 2011-10-13 2013-05-23 Sumitomo Chemical Co Ltd Compound, resin, resist composition and method for preparing resist pattern
JP2013137513A (en) * 2011-11-03 2013-07-11 Rohm & Haas Electronic Materials Llc Methods of forming photolithographic patterns by negative tone development
JP2013256658A (en) * 2012-05-18 2013-12-26 Sumitomo Chemical Co Ltd Resin, resist composition and method for producing resist pattern
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