JP2017088848A - Polymer compound, radiation-sensitive composition and pattern forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymer compound that can give a fine pattern with high sensitivity, a resist material and a radiation-sensitive composition comprising the compound, and a resist pattern forming method.SOLUTION: The polymer compound has a calixarene ring having a double-toroidal structure in which two resorcinol type calixarene rings are bonded to each other at 1 to 8 sites by a crosslinking group in a resorcinol moiety of a structural element in the calixarene ring, 0 to 7 of non-binding resorcinol moieties are present per one calixarene ring, and at least one crosslinking group has an acid dissociable moiety.SELECTED DRAWING: None

Description

  The present invention relates to a polymer compound, a radiation-sensitive composition using the same, and a resist pattern forming method.

  With the miniaturization of semiconductor elements, for example, development of lithography processes using, for example, extreme ultraviolet light (13.5 nm) or electron beams has been vigorously advanced. As base materials for the bases of chemically sensitized positive resists corresponding to these, novolak-type phenolic resins and polyhydroxystyrene-based resins (meth) acrylic acid-based resins, which are polymeric resist materials, are mainly studied. ing. However, the polymer resist material has a large molecular weight of about 10,000 to 100,000 and a wide molecular weight distribution. For this reason, in lithography using a polymer resist material, there is a problem that roughness occurs on the surface of a fine pattern. Therefore, recently, the development of compounds in which acid-dissociable functional groups that are decomposed by the action of acids are introduced into polyphenolic compounds and calixarene compounds, which are low-molecular resist materials, has been actively developed. However, there are reports that reduce the roughness of fine patterns. In addition, calixarene compounds used as low-molecular-weight resist materials have a rigid cyclic structure in the main skeleton, and therefore have sufficient heat resistance required to form patterns, and thus are promising. .

  As the acid-dissociable functional group, a monofunctional alkoxymethyl group, an alkoxyethyl group, and a tertiary alkoxy group are mainly used (for example, see Patent Document 1 below).

  In addition, studies using polyfunctional acid-dissociable functional groups have been actively conducted for the purpose of reducing the roughness of patterns obtained using polymer materials and suppressing pattern collapse (for example, see Patent Documents 2 to 7 below). .

  In addition, a main-chain-breaking positive resist material has been proposed by reacting a polyfunctional acid-dissociable functional group with a calixarene compound having a rigid cyclic structure (see, for example, Patent Document 8).

JP 2009-173623 A Japanese Patent Laid-Open No. 11-344808 JP 2000-098613 A JP 2005-308977 A JP 2006-2073 A JP 2006-3848 A JP 2007-206371 A International Publication No. 2012/014435

  However, the compound introduced with an acid-dissociable functional group described in Patent Document 1 has a problem that the resulting fine pattern tends to collapse. In addition, the resist material described in Patent Document 8 has room for improvement from the viewpoint that resolution is limited.

  An object of the present invention is to provide a polymer compound capable of obtaining a highly sensitive and fine pattern, a radiation-sensitive composition containing the same, and a pattern forming method.

As a result of intensive studies to solve the above problems, the present inventors have found that a polymer having a specific structure can solve the above problems, and have arrived at the present invention.
That is, the present invention is as follows.

<1> A polymer compound containing a unit structure represented by the following general formula (1).

General formula (1)
(In the general formula (1), m ₁ is an integer of ₁ to 8, n ₁ is an integer of 0 to 7, m ₁ + n ₁ = an integer of 4 to 8, and m ₂ is 1 to 8. N ₂ is an integer of 0 to 7, m ₂ + n ₂ = an integer of 4 to 8, y is independently an integer of 0 to 2, and R ¹ is independently a hydroxyl group A substituted or unsubstituted linear group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, Alternatively, a halogen atom, R ³ each independently represent a hydrogen atom, a substituted or unsubstituted straight, cyclic alkyl, branched or C3-20 having 3 to 20 carbon atoms group one, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, indicated R ² are each independently the following general formula (2) It is a structure of However, .R ⁵ having at least one R ² is an acid dissociable portion, ^{hydroxyl, -O-R 2 -O -.} *, (* Indicates the binding site between the unit structure.) Or —O—R ² —O—R ⁵⁵ (R ⁵⁵ is other R ⁵ in the general formula (1)), and R ⁶ is a hydroxyl group or —O—R ² —O— *. Yes (* indicates a binding site between the unit structures)

General formula (2)
(In the general formula (2), R ⁴ is a substituted or unsubstituted C 1-20 linear, C 3-20 branched or C 3-20 cyclic alkylene group, or It is a substituted or unsubstituted arylene group having 6 to 20 carbon atoms.)

<2> In the general formula (1), R ³ is a substituted or unsubstituted straight chain having 1 to 10 carbon atoms, a branched chain having 3 to 20 carbon atoms, or a cyclic alkyl group having 3 to 20 carbon atoms, or The polymer compound according to <1>, which is a substituted or unsubstituted aryl group having 6 to 10 carbon atoms.
<3> A radiation-sensitive composition comprising the polymer compound according to <1> or <2>.
<4> The radiation-sensitive composition according to <3>, further including a solvent.
<5> Using the radiation-sensitive composition according to <3> or <4>, a film forming step of forming a film on a substrate, an exposure step of exposing the film, and exposure in the exposure step A patterning method comprising: developing the formed film to form a pattern.

  ADVANTAGE OF THE INVENTION According to this invention, the high sensitivity and the high molecular compound from which a fine pattern is obtained, the resist material containing the same, a radiation sensitive composition, and the resist pattern formation method can be provided.

1 is a diagram showing a ¹ H-NMR spectrum of a compound obtained in Example 1. FIG. 1 is a diagram showing an IR spectrum of a compound obtained in Example 1. FIG.

  Hereinafter, embodiments of the present invention will be described (hereinafter may be referred to as “this embodiment”). In addition, this embodiment is an illustration for demonstrating this invention, and this invention is not limited only to this embodiment.

[Polymer compound]
The polymer compound of this embodiment is a polymer containing a unit structure represented by the following general formula (1).

General formula (1)
(In the general formula (1), m ₁ is an integer of ₁ to 8, n ₁ is an integer of 0 to 7, m ₁ + n ₁ = an integer of 4 to 8, and m ₂ is 1 to 8. N ₂ is an integer of 0 to 7, m ₂ + n ₂ = an integer of 4 to 8, y is independently an integer of 0 to 2, and R ¹ is independently a hydroxyl group A substituted or unsubstituted linear group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, Alternatively, a halogen atom, R ³ each independently represent a hydrogen atom, a substituted or unsubstituted straight, cyclic alkyl, branched or C3-20 having 3 to 20 carbon atoms group one, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, indicated R ² are each independently the following general formula (2) It is a structure of However, .R ⁵ having at least one R ² is an acid dissociable portion, ^{hydroxyl, -O-R 2 -O -.} *, (* Indicates the binding site between the unit structure.) Or —O—R ² —O—R ⁵⁵ (R ⁵⁵ is other R ⁵ in the general formula (1)), and R ⁶ is a hydroxyl group or —O—R ² —O— *. Yes (* indicates a binding site between the unit structures)

General formula (2)
(In the general formula (2), R ⁴ is a substituted or unsubstituted C 1-20 linear, C 3-20 branched or C 3-20 cyclic alkylene group, or It is a substituted or unsubstituted arylene group having 6 to 20 carbon atoms.)

  Since the polymer compound of the present embodiment has a specific structure as described above, it has high sensitivity and can provide a fine pattern when used as a radiation-sensitive composition. Furthermore, the polymer compound of the present embodiment can have improved solubility in a safe solvent, if necessary, can be easily controlled, and can easily stabilize the quality.

First, the structure of the polymer compound of this embodiment will be described. As shown below, the polymer compound of the present embodiment includes a unit structure (hereinafter “C”) represented by the general formula (1). The number of unit structures represented by the general formula (1) contained in the polymer compound of the present embodiment is not particularly limited, but is preferably 1 to 100 from the viewpoint of resolution, and 1 to 50 from the viewpoint of roughness. Is more preferable, and 1 to 10 is particularly preferable from the viewpoint of sensitivity. When the polymer compound of the present embodiment has a plurality of unit structures, the unit structures are bonded to each other via “—O—R ² —O— *” in R ⁵ or R ⁶ in the general formula (1). That is, when the polymer compound of the present embodiment has a plurality of unit structures, the structural unit represented by the general formula (1) has —O—R ² —O— * as R ⁵ or R ⁶ . The polymer compound of the present embodiment can contain structural units other than the unit structure represented by the general formula (1) as long as the effects of the present invention are not impaired. Examples of the unit structure other than the unit structure represented by the general formula (1) include a structure composed only of an upper or lower annular structure described later. In addition, the polymer compound of the present embodiment may be composed of only the same type of unit structure, or may include two or more types of structural units.

In addition, the unit structure in the polymer compound of the present embodiment includes two cyclic structures. In the present specification, for the sake of convenience, in the general formula (1), the annular structure positioned in the upper direction of the paper is referred to as “upper annular structure” (the “A”), and the annular structure positioned in the lower direction of the paper is referred to as the “lower annular structure” (described above). "B"). However, in an actual compound, the upper ring structure and the lower ring structure are not distinguished. Each cyclic structure has two types of benzene ring structures. For example, the upper ring structure includes a benzene ring structure having R ⁵ and a portion bonded to the lower ring structure (the “A1”) and a benzene ring structure having R ⁶ (the “A2”). Similarly, the lower cyclic structure includes a benzene ring structure having the portion bonded to the upper cyclic structure and R ⁵ (the “B1”) and a benzene structure having R ⁶ (the “B2”). In the present specification, these are appropriately referred to as benzene ring structures A1 to B2.

In the polymer compound of the present embodiment, the upper ring structure and the lower ring structure are bonded to each other with a benzene ring structure to form one ring structure. That is, m ₁ benzene ring structures A1 and n ₁ benzene ring structures A2 combine to form an upper ring structure. Similarly, the lower ring structure is composed of m ₂ benzene ring structures B1 and n ₂ benzene ring structures B2. At this time, an arrangement of m ₁ benzene ring structures A1 and n ₁ benzene ring structures A2 in the upper ring structure, and m ₂ benzene ring structures B1 and n ₂ benzene ring structures B2 in the lower ring structure The arrangement of is arbitrary, and may be arranged with regularity or may be arranged at random.

In the general formula (1), m ₁ is an integer from 1 to 8, n ₁ is an integer of 0-7, an integer of m ₁ + n ₁ = 4~8. Although not particularly limited, m ₁ is preferably an integer of 2 to 6, n ₁ is preferably an integer of 2 to 6, and m ₁ + n ₁ is preferably an integer of 2 to 8.
In the general formula (1), m ₂ is an integer from 1 to 8, n ₂ is an integer of 0-7, an integer of m ₂ + n ₂ = 4~8. Although not particularly limited, m ₂ is preferably an integer of ₂ to 6, n ₂ is preferably an integer of ₂ to 6, and m ₁ + n ₁ is preferably an integer of 2 to 8.
When the polymer compound of the present embodiment includes a plurality of structural units represented by the general formula (1), m ¹ , m ² , n ¹ and n ² in each structural unit are the same among the structural units. They may be different from each other.

  For example, in the upper cyclic structure, the benzene ring structures A1 and A2 can use the 3-position carbon and the 5-position carbon of the benzene ring as a binding site for constituting the upper cyclic structure. The same applies to the benzene ring structures B1 and B2 in the lower ring structure.

Each R ¹ is independently a hydroxyl group, a substituted or unsubstituted linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 3 to 20 carbon atoms; substituted or unsubstituted carbon An aryl group of 6 to 20; or a halogen atom. Moreover, y shows the integer of 0-2 each independently.

Examples of the unsubstituted linear alkyl group having 1 to 20 carbon atoms include, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, hexadecyl group, An octadecyl group etc. are mentioned.
Examples of the substituted linear alkyl group having 1 to 20 carbon atoms include a fluoromethyl group, a 2-hydroxyethyl group, a 3-cyanopropyl group, and a 20-nitrooctadecyl group.
As said unsubstituted or substituted linear alkyl group, a C1-C10 thing can be used preferably.

Examples of the unsubstituted alkyl group having 3 to 20 carbon atoms include isopropyl group, isobutyl group, tertiary butyl group, neopentyl group, 2-hexyl group, 2-octyl group, 2-decyl group, 2- A dodecyl group, 2-hexadecyl group, 2-octadecyl group, etc. are mentioned.
Examples of the substituted alkyl group having 3 to 20 carbon atoms include 1-fluoroisopropyl group and 1-hydroxy-2-octadecyl group.

Examples of the unsubstituted C3-C20 cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, a cyclodecyl group, a cyclododecyl group, a cyclohexadecyl group, and a cyclooctadecyl group. Etc.
Examples of the substituted C3-C20 cyclic alkyl group include a 2-fluorocyclopropyl group and a 4-cyanocyclohexyl group.

Examples of the unsubstituted aryl group having 6 to 20 carbon atoms include a phenyl group and a naphthyl group.
Examples of the substituted aryl group having 6 to 20 carbon atoms include 4-isopropylphenyl group, 4-cyclohexylphenyl group, 4-methylphenyl group, 6-fluoronaphthyl group and the like. As said unsubstituted or substituted aryl group, a C6-C10 thing can be used preferably.

  Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  In this specification, “substitution” means that, unless otherwise defined, one or more hydrogen atoms in a functional group are a halogen atom, a hydroxyl group, a cyano group, a nitro group, a heterocyclic group, or a carbon number of 1 -20 linear aliphatic hydrocarbon group, branched aliphatic hydrocarbon group having 3 to 20 carbon atoms, cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, carbon number 7-30 aralkyl group, C1-C20 alkoxy group, C0-20 amino group, C2-C20 alkenyl group, C1-C20 acyl group, C2-C20 alkoxy It means that it is substituted with a carbonyl group, an alkylyl group having 1 to 20 carbon atoms, an aryloyloxy group having 7 to 30 carbon atoms, or an alkylsilyl group having 1 to 20 carbon atoms.

In the general formula (1), each R ³ is independently a hydrogen atom, a substituted or unsubstituted straight chain having 1 to 20 carbon atoms, a branched chain having 3 to 20 carbon atoms, or a cyclic alkyl having 3 to 20 carbon atoms. Or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms.

In R ^3, a substituted or unsubstituted straight, cyclic alkyl group branched or C3-20 having 3 to 20 carbon atoms; and a substituted or unsubstituted carbon atoms 6 Examples of the aryl group of 20 include the same as those exemplified for R ¹ .

In the general formula (1), R ² is each independently R ² is independently any one of the structures represented by the general formula (2). However, at least one R ² has an acid dissociable portion. When R ² has an acid-dissociable portion, it can function as a main-chain-breaking positive resist material or negative resist material in which a polymer is cleaved by the action of an acid.

In the general formula (2), R ⁴ represents a substituted or unsubstituted linear chain having 1 to 20 carbon atoms, a branched chain having 3 to 20 carbon atoms, or a cyclic alkylene group having 3 to 20 carbon atoms, or substituted or unsubstituted It is an unsubstituted arylene group having 6 to 20 carbon atoms.

Examples of the unsubstituted linear alkylene group having 1 to 20 carbon atoms include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, an octylene group, a decylene group, a dodecylene group, a hexadecylene group, An octadecylene group etc. are mentioned.
Examples of the substituted C1-C20 linear alkylene group include a fluoromethylene group, a 2-hydroxyethylene group, a 3-cyanopropylene group, and a 20-nitrooctadecylene group.

Examples of the unsubstituted alkylene group having 3 to 20 carbon atoms include isopropylene group, isobutylene group, tertiary butylene group, neopentylene group, 2-hexylene group, 2-octylene group, 2-decylene group, 2 -Dodecylene group, 2-hexadecylene group, 2-octadecylene group, etc. are mentioned.
Examples of the substituted alkylene group having 3 to 20 carbon atoms include 1-fluoroisopropylene group and 1-hydroxy-2-octadecylene group.

The unsubstituted C3-C20 cyclic alkylene group is, for example, a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cyclooctylene group, a cyclodecylene group, a cyclododecylene group, or a cyclohexadecylene group. And cyclooctadecylene group.
Examples of the substituted C3-C20 cyclic alkylene group include 2-fluorocyclopropylene group and 4-cyanocyclohexylene group.

Examples of the unsubstituted arylene group having 6 to 20 carbon atoms include a phenylene group and a naphthylene group.
Examples of the substituted arylene group having 6 to 20 carbon atoms include a 4-isopropylphenylene group, a 4-cyclohexylphenylene group, a 4-methylphenylene group, and a 6-fluoronaphthylene group.

In the general formula (1), at least one R ² has an acid dissociable portion. In this specification, the “acid-dissociable site” refers to a site that is cleaved in the presence of an acid to cause a change in an alkali-soluble group or the like. Although it does not specifically limit as an alkali-soluble group, For example, a phenolic hydroxyl group, a carboxyl group, a sulfonic acid group, a hexafluoroisopropanol group etc. are mentioned, A phenolic hydroxyl group and a carboxyl group are preferable, and a phenolic hydroxyl group is especially preferable. Examples of the general formula (2) having the acid dissociable portion include the following.

R ⁵ in the general formula (1) is a hydroxyl group, —O—R ² —O— * (* represents a bonding site between the unit structures), or —O—R ² —O—R ⁵⁵ . (R ⁵⁵ is another R ⁵ in the general formula (1)). That is, in the benzene ring structures A1 and B1, at least one “—O—R ² —O—” on the benzene ring connects the upper ring structure and the lower ring structure in the same unit structure. In addition, the other bond (that is, R ⁵ ) of the benzene ring structures A1 and B1 may be a hydroxyl group (OH—), or “—O—R ² — bonded to another unit structure with“ * ”. O— * ”or“ —O—R ² —O—R ⁵⁵ ”, which is combined with the other R ⁵ in the upper ring structure or the lower ring structure in the same unit structure, The upper annular structure and the lower annular structure may be combined in the structure.
R ⁶ in the general formula (1) is a hydroxyl group or —O—R ² —O— * (* represents a bonding site between the unit structures).

As described above, when the polymer compound of the present embodiment has a plurality of unit structures, at least one of R ⁵ and R ⁶ in the unit structure represented by at least one general formula (1) is “—O—R ^2. -O- * ", and a plurality of unit structures are bonded through R ⁵ or R ⁶ . In —O—R ² —O— *, “*” represents a binding site between unit structures. For example, when the polymer compound of this embodiment has two unit structures represented by the general formula (1), at least one of R ⁵ and R ^{6 in} the unit structure represented by one general formula (1). The * part in (—O—R ² —O— *) is bonded to the carbon atom constituting the benzene ring in the unit structure represented by the other general formula (1).

In the general formula (1), when R ⁵ is “—O—R ² —O—R ⁵⁵ ”, that is, one benzene ring structure A1 or B1 connects the upper ring structure and the lower ring structure. to If "-O-R ² -O-" a has two, two "-O-R ² -O-" may be bonded with other different benzene ring structures, respectively, It may be bonded to the same benzene ring structure.
Furthermore, a plurality of R ⁵ or R ⁶ is - if "O-R ² -O- *" have, each of R ⁵ to R ⁶ through a "-O-R ² -O- *" It may be bonded to the same other unit structure, or may be bonded to different unit structures.

  The polymer compound of the present embodiment can be obtained, for example, by reacting a compound represented by the following general formula (3) with any compound consisting of the group represented by the following general formula (4). .

General formula (3)
(In general formula (3), R ¹ , R ³ , m ₁ , n ₁ and y have the same meanings as in general formula (1).)

General formula (4)
(In General Formula (4), R ⁴ has the same meaning as in General Formula (2), X ¹ is a halogen atom, and X ² is a halogen atom or a hydroxyl group.)

Examples of the halogen atom represented by X ¹ and X ² in the general formula (4) are the same as those represented by R ¹ described above.

  The compound represented by the formula (3) is preferably one compound selected from the group represented by the following compounds.

(3-1)

  The compound represented by the formula (4) is preferably one compound selected from the group represented by the following compounds.

(4-1)
(In formula (4-1), R ⁴ has the same meaning as in formula (2)).

From the viewpoint of heat resistance, R ⁴ described above preferably includes one group selected from the group represented by the following formula (4-2).

Formula (4-2)

  The reaction of the compound represented by the general formula (3) and any one of the compounds represented by the general formula (4) is not particularly limited, but if necessary, both compounds are dissolved in a solvent, and a catalyst is obtained. It is preferable to carry out the reaction in the presence of

Examples of the solvent used in the reaction of the compound represented by the general formula (3) and any one of the compounds represented by the general formula (4) include acetone, tetrahydrofuran (THF), propylene glycol monomethyl ether acetate. And aprotic solvents such as dimethylacetamide and N-methylpyrrolidone. For example, the compound represented by the general formula (3) is dissolved or suspended in these solvents. Subsequently, divinyl alkyl ether such as divinyloxymethyladamantane (a compound represented by the general formula (4)) is added, and 20 to 20 at atmospheric pressure in the presence of an acid catalyst such as trifluoroacetic acid or pyridinium p-toluenesulfonate. 6
The reaction is carried out at 0 ° C. for 6 to 72 hours. The reaction solution is neutralized with an alkali compound and added to distilled water to precipitate a white solid, and then the separated white solid is washed with distilled water and dried to obtain the intended polymer compound.

  Further, for example, a compound represented by the general formula (3) is dissolved or suspended in an aprotic solvent, and then an alkyl halide such as ethyl chloromethyl ether (compound represented by the general formula (4)) is added, and carbonic acid is added. The reaction is carried out at 20 to 110 ° C. for 6 to 72 hours at normal pressure in the presence of an alkali catalyst such as potassium. The reaction solution is neutralized with an acid such as hydrochloric acid and added to distilled water to precipitate a white solid, and then the separated white solid is washed with distilled water and dried to obtain the desired polymer compound. .

  In the present embodiment, it is preferable to synthesize a polymer compound using two or more compounds represented by the general formula (3) and / or any compound consisting of the group represented by the general formula (4). By using two or more compounds represented by the general formula (3) and / or any compound consisting of the group represented by the general formula (4), the solubility of the resulting polymer in a semiconductor safety solvent is improved. .

  In order to reduce the amount of residual metal in the polymer, purification treatment may be performed as necessary. Further, when the acid catalyst remains, generally, the storage stability of the radiation-sensitive composition may be reduced, or when the basic catalyst remains, generally, the sensitivity of the radiation-sensitive composition may be reduced. You may perform the refinement | purification aiming at the reduction. Purification can be performed by a known method as long as the polymer is not modified, and is not particularly limited. For example, a method of washing with water, a method of washing with an acidic aqueous solution, a method of washing with a basic aqueous solution, or an ion exchange resin. The method of processing, the method of processing by silica gel column chromatography, etc. are mentioned. These purification methods are more preferably performed in combination of two or more. Acidic aqueous solution, basic aqueous solution, ion exchange resin, and silica gel column chromatography are optimal depending on the metal to be removed, the amount and type of acidic compound and / or basic compound, the type of dissolution inhibitor to be purified, etc. Can be appropriately selected. For example, as acidic aqueous solution, hydrochloric acid, nitric acid, acetic acid aqueous solution having a concentration of 0.01 to 10 mol / L, aqueous ammonia solution having a concentration of 0.01 to 10 mol / L as basic aqueous solution, cation exchange resin as ion exchange resin, For example, Amberlyst 15J-HG Dry made by Organo can be mentioned. You may dry after refinement | purification. Drying can be performed by a known method, and is not particularly limited, and examples thereof include a vacuum drying method and a hot air drying method under conditions where the polymer is not denatured.

  The polymer compound of the present embodiment has a low sublimation property under normal pressure at 100 ° C. or lower, preferably 120 ° C. or lower, more preferably 130 ° C. or lower, further preferably 140 ° C. or lower, particularly preferably 150 ° C. or lower. preferable. The low sublimation property means that in thermogravimetric analysis, the weight loss when held at a predetermined temperature for 10 minutes is 10%, preferably 5%, more preferably 3%, still more preferably 1%, particularly preferably 0.1. % Or less is preferable. Since the sublimation property is low, it is possible to prevent exposure apparatus from being contaminated by outgas during exposure. Further, a good pattern shape can be provided with low line edge roughness (hereinafter, sometimes simply referred to as “LER”).

  The polymer compound of the present embodiment preferably satisfies F <3.0 (F represents the total number of atoms / (total number of carbons−total number of oxygen atoms)), and more preferably satisfies F <2.5. By satisfying the above conditions, dry etching resistance can be improved.

  A non-acid dissociable functional group may be introduced into at least one phenolic hydroxyl group and / or carboxyl group of the polymer compound as long as the effects of the present invention are not impaired. The non-acid-dissociable functional group refers to a characteristic group that does not cleave in the presence of an acid and does not generate an alkali-soluble group. For example, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, cyano, which is not decomposed by the action of an acid And a functional group selected from the group consisting of a group, a nitro group, a hydroxyl group, a heterocyclic group, a halogen atom, a carboxyl group, an alkylsilyl group having 1 to 20 carbon atoms, and derivatives thereof.

The number average molecular weight (Mn) in terms of polystyrene of the polymer compound of the present embodiment is preferably 1000 to 50000, more preferably 1500 to 10000, and particularly preferably 2500 to 7500. When the number average molecular weight of the polymer compound of the present embodiment is within the above range, the pattern collapse can be further suppressed and the resolution can be improved while maintaining the film formability required for the resist.
Further, the dispersity (weight average molecular weight / number average molecular weight (hereinafter sometimes simply referred to as “Mw / Mn”) of the polymer compound of the present embodiment is preferably Mw / Mn <1.7. Preferably, Mw / Mn <1.5, more preferably Mw / Mn <1.3 from the viewpoint of sensitivity, more preferably Mw / Mn <1.2 from the viewpoint of low roughness, Preferably, Mw / Mn <1.1.

Particularly preferred as the polymer compound of the present embodiment is that the compound represented by the general formula (3) reacts with one of the compounds represented by the general formula (4), and then one general compound A compound represented by the following general formula (5), obtained by reacting a compound represented by the formula (3).
Since it has many such tube-like structures, the polymer compound of this embodiment is not gelled, has excellent solvent solubility, and has a large number of pores, so it is very sensitive.

General formula (5)
(In the general formula (5), R ¹ , R ² , R ³ , and y are as defined above and the general formula (1), and n is 4-8.
Is an integer. )

  Moreover, it is preferable that the high molecular compound of this embodiment is a compound represented by the following general formula (X).

Formula (X)

  Specific examples of the polymer compound of the present embodiment are shown below. However, the polymer compound of the present embodiment is not limited to the following specific examples.

  When the polymer compound of the present embodiment is used, the strength of the resist pattern obtained and the adhesion to the substrate are improved, so that the problem of pattern collapse seen in low molecular weight systems can be suppressed. Moreover, since the molecular weight of the polymer compound of the present embodiment is reduced due to the elimination of the crosslinkable protecting group in the exposed portion, the roughness of the resist pattern can be reduced as in the case of the low molecular weight system. In addition, the polymer compound of the present embodiment has high heat resistance and is amorphous, so that it has excellent film forming properties, no sublimation property, excellent developability, etching resistance, and the like. It can be suitably used as the main component (base material).

  Since the polymer compound of the present embodiment has a tube-like structure, it does not gel, has excellent solvent solubility, and has a large number of pores, so it has very high sensitivity. Also, in terms of production, the compound represented by the above general formula (3) is reacted with any one of the compounds represented by the general formula (4) from which industrial products can be easily obtained by a known method. By doing so, it can be manufactured in a high yield, so that it is extremely excellent in practicality.

[Radiation sensitive composition]
The radiation sensitive composition of this embodiment has the polymer compound of this embodiment described above. The radiation sensitive composition of this embodiment may contain the solvent as needed. The radiation-sensitive composition of this embodiment is preferably irradiated with any radiation selected from the group consisting of visible light, ultraviolet light, excimer laser, electron beam, extreme ultraviolet light (EUV), X-ray, and ion beam. An acid generator (C) that generates an acid directly or indirectly, an acid diffusion controller (E), and a solvent can be included.

  The radiation sensitive composition of the present embodiment can form an amorphous film by a method such as spin coating. In addition, the radiation-sensitive composition of the present embodiment can make either a positive resist pattern or a negative resist pattern depending on the type of developer used. For example, when an alkaline developer is used, a positive pattern is obtained. When an organic developer is used, a negative pattern is obtained.

  In the case of forming a positive resist pattern, the dissolution rate of the amorphous film formed by spin-coating the radiation-sensitive composition of the present embodiment in a developing solution at 23 ° C. is preferably 5 Å / sec or less, and 0.05 to 5 Å / Sec is more preferable, and 0.0005 to 5 g / sec is more preferable. When the dissolution rate is 5 kg / sec or less, a resist insoluble in the developer can be obtained. In addition, when the radiation-sensitive composition of the present embodiment has a dissolution rate of 0.0005 kg / sec or more, resolution may be improved. This is presumably because the contrast between the exposed portion dissolved in the developer and the unexposed portion not dissolved in the developer increases due to the change in solubility of the polymer compound of this embodiment before and after exposure. . Moreover, when the radiation sensitive composition of this embodiment is used, there is an effect of reducing line edge roughness and reducing defects.

When forming a negative resist pattern, the dissolution rate of the amorphous film formed by spin-coating the radiation-sensitive composition of the present embodiment in a developing solution at 23 ° C. is preferably 10 Å / sec or more. When the dissolution rate is 10 Å / sec or more, it is easily dissolved in a developer and more suitable for a resist. If the dissolution rate is 10 Å / sec or more, the resolution may be improved. This is presumed to be because the micro surface portion of the polymer compound of the present embodiment is dissolved and the line edge roughness is reduced. Moreover, when the radiation sensitive composition of this embodiment is used, there exists an effect of reducing a defect.
The dissolution rate is determined by immersing the amorphous film in a developer at a temperature of 23 ° C. for a predetermined time, and measuring the film thickness before and after the immersion by a known method such as visual observation, an ellipsometer, or a QCM method, It can be calculated based on the measured value.

  When forming a positive resist pattern, the amorphous film formed by spin-coating the radiation-sensitive composition of the present embodiment is exposed to 23 ° C. of a portion exposed by radiation such as KrF excimer laser, extreme ultraviolet light, electron beam or X-ray. The dissolution rate with respect to the developer in is preferably 10 に お け る / sec or more. When the dissolution rate is 10 Å / sec or more, it is easily dissolved in a developer and more suitable for a resist. If the dissolution rate is 10 Å / sec or more, the resolution may be improved. This is presumed to be because the micro surface portion of the polymer compound of this embodiment is dissolved and the line edge roughness is reduced. Moreover, when the radiation sensitive composition of this embodiment is used, there exists an effect of reducing a defect.

  When forming a negative resist pattern, the amorphous film formed by spin-coating the radiation-sensitive composition of this embodiment is exposed to 23 ° C. of the portion exposed by radiation such as KrF excimer laser, extreme ultraviolet light, electron beam or X-ray. The dissolution rate in the developing solution is preferably 5 Å / sec or less, more preferably 0.05 to 5 Å / sec, and further preferably 0.0005 to 5 Å / sec. When the dissolution rate is 5 kg / sec or less, a resist insoluble in the developer can be obtained. In addition, when the dissolution rate is 0.0005 kg / sec or more, the resolution may be improved. This is presumably because the contrast of the unexposed portion dissolved in the developer and the exposed portion not dissolved in the developer increases the contrast due to the change in the solubility of the polymer compound of the present embodiment before and after exposure. . Moreover, when the radiation sensitive composition of this embodiment is used, there is an effect of reducing line edge roughness and reducing defects.

  The radiation sensitive composition of this embodiment can be comprised as solid content 1-80 mass% and 20-99 mass% of solvent, for example, Preferably 1-50 mass% of solid content and 50-99 of solvent are preferable. More preferably, the solid content is 2 to 40% by mass and the solvent is 60 to 98% by mass, and particularly preferably the solid content is 2 to 10% by mass and the solvent is 90 to 98% by mass.

  Content in the radiation sensitive composition of the high molecular compound of this embodiment is 10-90 mass% with respect to solid content total mass, Preferably it is 30-90 mass%, More preferably, it is 50-80 mass. %, Particularly preferably 70 to 75% by mass. When the content of the polymer compound of the present embodiment in the radiation-sensitive composition is such a blending ratio as described above, higher resolution is obtained and the line edge roughness is reduced.

(Acid generator (C))
The radiation-sensitive composition of this embodiment is directly or indirectly oxidized by irradiation with any radiation selected from visible light, ultraviolet light, excimer laser, electron beam, extreme ultraviolet light (EUV), X-ray, and ion beam. It is preferable to contain at least one acid generator (C) that generates oxygen.
In this case, in the radiation-sensitive composition of the present embodiment, the content of the acid generator (C) is preferably 0.001 to 50% by mass and more preferably 10 to 37.5% by mass of the total mass of the solid content. Preferably, 10 to 30% by mass is particularly preferable. By using the acid generator (C) within the content range, a pattern profile with higher sensitivity and lower edge roughness can be obtained.
In the resist composition of this embodiment, the acid generation method is not limited as long as an acid is generated in the system. If excimer laser is used instead of ultraviolet rays such as g-line and i-line, finer processing is possible, and if high-energy rays are used, electron beam, extreme ultraviolet rays, X-rays, ion beam, further fine processing Is possible.

  The acid generator (C) is preferably at least one selected from the group consisting of compounds represented by the following formulas (7-1) to (7-8).

Formula (7-1)
(In formula (7-1), R ^{13 s} may be the same or different, and each independently represents a hydrogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic group. An alkoxy group, a hydroxyl group or a halogen atom; X ⁻ is a sulfonate ion or a halide ion having an alkyl group, an aryl group, a halogen-substituted alkyl group or a halogen-substituted aryl group.

The compound represented by the formula (7-1) includes triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, diphenyltolylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium perfluoro-n-. Octanesulfonate, diphenyl-4-methylphenylsulfonium trifluoromethanesulfonate, di-2,4,6-trimethylphenylsulfonium trifluoromethanesulfonate, diphenyl-4-t-butoxyphenylsulfonium trifluoromethanesulfonate, diphenyl-4-t-butoxyphenyl Sulfonium nonafluoro-n-butanesulfonate, diphenyl-4-hydroxyphenylsulfonium trifluoromethanes Phonate, bis (4-fluorophenyl) -4-hydroxyphenylsulfonium trifluoromethanesulfonate, diphenyl-4-hydroxyphenylsulfonium nonafluoro-n-butanesulfonate, bis (4-hydroxyphenyl) -phenylsulfonium trifluoromethanesulfonate, tri ( 4-methoxyphenyl) sulfonium trifluoromethanesulfonate, tri (4-fluorophenyl) sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfoniumbenzenesulfonate, diphenyl-2,4,6-trimethylphenyl-p-toluene Sulfonate, diphenyl-2,4,6-trimethylphenylsulfonium-2-trifluoromethylben Zensulfonate, diphenyl-2,4,6-trimethylphenylsulfonium-4-trifluoromethylbenzenesulfonate, diphenyl-2,4,6-trimethylphenylsulfonium-2,4-difluorobenzenesulfonate, diphenyl-2,4,6 -Trimethylphenylsulfonium hexafluorobenzenesulfonate, diphenylnaphthylsulfonium trifluoromethanesulfonate, diphenyl-4-hydroxyphenylsulfonium-p-toluenesulfonate, triphenylsulfonium 10-camphorsulfonate, diphenyl-4-hydroxyphenylsulfonium 10-camphorsulfonate and cyclo At least one selected from the group consisting of (1,3-perfluoropropanedisulfone) imidate It is preferable that a class.

Formula (7-2)
(In formula (7-2), R ^{14 s} may be the same or different, and each independently represents a hydrogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic group. Represents an alkoxy group, a hydroxyl group or a halogen atom, and X ⁻ has the same meaning as in formula (7-1).

  The compound represented by the formula (7-2) includes bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium nonafluoro-n-butanesulfonate, bis (4-t -Butylphenyl) iodonium perfluoro-n-octanesulfonate, bis (4-t-butylphenyl) iodonium p-toluenesulfonate, bis (4-t-butylphenyl) iodoniumbenzenesulfonate, bis (4-t-butylphenyl) Iodonium-2-trifluoromethylbenzenesulfonate, bis (4-t-butylphenyl) iodonium-4-trifluoromethylbenzenesulfonate, bis (4-t-butylphenyl) iodonium-2,4-difluorobenzenesulfonate, bis ( 4-t Butylphenyl) iodonium hexafluorobenzenesulfonate, bis (4-t-butylphenyl) iodonium 10-camphorsulfonate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium perfluoro-n-octanesulfonate, Diphenyliodonium p-toluenesulfonate, diphenyliodoniumbenzenesulfonate, diphenyliodonium10-camphorsulfonate, diphenyliodonium-2-trifluoromethylbenzenesulfonate, diphenyliodonium-4-trifluoromethylbenzenesulfonate, diphenyliodonium-2,4-difluorobenzene Sulfonate, diphenyl Iodonium hexafluorobenzenesulfonate, di (4-trifluoromethylphenyl) iodonium trifluoromethanesulfonate, di (4-trifluoromethylphenyl) iodonium nonafluoro-n-butanesulfonate, di (4-trifluoromethylphenyl) iodonium per From fluoro-n-octanesulfonate, di (4-trifluoromethylphenyl) iodonium p-toluenesulfonate, di (4-trifluoromethylphenyl) iodoniumbenzenesulfonate and di (4-trifluoromethylphenyl) iodonium 10-camphorsulfonate Preferably, at least one selected from the group consisting of:

Formula (7-3)
(In formula (7-3), Q represents an alkylene group, an arylene group or an alkoxylene group, and R ¹⁵ represents an alkyl group, an aryl group, a halogen-substituted alkyl group or a halogen-substituted aryl group.)

  The compound represented by the formula (7-3) includes N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- ( Trifluoromethylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) naphthylimide, N- (10-camphorsulfonyloxy) Succinimide, N- (10-camphorsulfonyloxy) phthalimide, N- (10-camphorsulfonyloxy) diphenylmaleimide, N- (10-camphorsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2 , 3-Dicarboximide, N- 10-camphorsulfonyloxy) naphthylimide, N- (n-octanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (n-octanesulfonyloxy) Naphthylimide, N- (p-toluenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (p-toluenesulfonyloxy) naphthylimide, N- (2 -Trifluoromethylbenzenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2-trifluoromethylbenzenesulfonyloxy) naphthylimide, N- (4 -Trifluoromethylbenzenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy Imido, N- (4-trifluoromethylbenzenesulfonyloxy) naphthylimide, N- (perfluorobenzenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (Perfluorobenzenesulfonyloxy) naphthylimide, N- (1-naphthalenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (1-naphthalenesulfonyloxy) Naphthylimide, N- (nonafluoro-n-butanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (nonafluoro-n-butanesulfonyloxy) naphthylimide, N- (perfluoro-n-octanesulfonyloxy) bicyclo [2.2.1] hept It is preferably at least one selected from 5-En 2,3-dicarboximide, and N- (perfluoro--n- C1-12alkyl oxy) group consisting naphthylimide.

Formula (7-4)
(In formula (7-4), R ^{16 s} may be the same or different, and each independently represents an optionally substituted linear, branched or cyclic alkyl group, an optionally substituted aryl group, A heteroaryl group substituted with or an aralkyl group optionally substituted.)

  The compound represented by the formula (7-4) is diphenyl disulfone, di (4-methylphenyl) disulfone, dinaphthyl disulfone, di (4-tert-butylphenyl) disulfone, di (4-hydroxyphenyl) disulfone. , Di (3-hydroxynaphthyl) disulfone, di (4-fluorophenyl) disulfone, di (2-fluorophenyl) disulfone and di (4-trifluoromethylphenyl) disulfone It is preferable.

Formula (7-5)
(In Formula (7-5), R ^{17 s} may be the same or different, and each independently represents an optionally substituted linear, branched or cyclic alkyl group, an optionally substituted aryl group, an arbitrary A heteroaryl group substituted with or an aralkyl group optionally substituted.)

  The compound represented by the formula (7-5) is α- (methylsulfonyloxyimino) -phenylacetonitrile, α- (methylsulfonyloxyimino) -4-methoxyphenylacetonitrile, α- (trifluoromethylsulfonyloxyimino). -Phenylacetonitrile, α- (trifluoromethylsulfonyloxyimino) -4-methoxyphenylacetonitrile, α- (ethylsulfonyloxyimino) -4-methoxyphenylacetonitrile, α- (propylsulfonyloxyimino) -4-methylphenylacetonitrile And at least one selected from the group consisting of α- (methylsulfonyloxyimino) -4-bromophenylacetonitrile.

Formula (7-6)

In formula (7-6), R ^{18 s} may be the same or different and are each independently a halogenated alkyl group having one or more chlorine atoms and one or more bromine atoms. The halogenated alkyl group preferably has 1 to 5 carbon atoms.

Formula (7-7)

Formula (7-8)

In formulas (7-7) and (7-8), R ¹⁹ and R ²⁰ are each independently an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, an n-propyl group or an isopropyl group, or a cyclopentyl group. , A cycloalkyl group such as a cyclohexyl group, an alkoxyl group having 1 to 3 carbon atoms such as a methoxy group, an ethoxy group, and a propoxy group, or an aryl group such as a phenyl group, a toluyl group, and a naphthyl group, preferably 6 to 10 carbon atoms An aryl group. L ¹⁹ and L ²⁰ are each independently an organic group having a 1,2-naphthoquinonediazide group. Specific examples of the organic group having a 1,2-naphthoquinonediazide group include a 1,2-naphthoquinonediazide-4-sulfonyl group, a 1,2-naphthoquinonediazide-5-sulfonyl group, and a 1,2-naphthoquinonediazide- A 1,2-quinonediazidosulfonyl group such as a 6-sulfonyl group can be mentioned as a preferable one. In particular, 1,2-naphthoquinonediazide-4-sulfonyl group and 1,2-naphthoquinonediazide-5-sulfonyl group are preferable. p is each independently an integer of 1 to 3, q is independently an integer of 0 to 4, and 1 ≦ p + q ≦ 5. J ¹⁹ is a single bond, a polymethylene group having 1 to 4 carbon atoms, a cycloalkylene group, a phenylene group, a group represented by the following formula (7-7-1), a carbonyl group, an ester group, an amide group or an ether group, Y ¹⁹ represents a hydrogen atom, an alkyl group, or an aryl group, and X ²⁰ each independently represents a group represented by the following formula (7-8-1).

Formula (7-7-1)

Formula (7-8-1)
(In the formula (7-8-1), respectively the Z ²² independently an alkyl group, a cycloalkyl group or an aryl group, R ²² is an alkyl group, a cycloalkyl group or an alkoxyl group, r is 0 to 3 Is an integer.)

  Other acid generators include bis (p-toluenesulfonyl) diazomethane, bis (2,4-dimethylphenylsulfonyl) diazomethane, bis (tert-butylsulfonyl) diazomethane, bis (n-butylsulfonyl) diazomethane, bis (isobutylsulfonyl) ) Diazomethane, bis (isopropylsulfonyl) diazomethane, bis (n-propylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (isopropylsulfonyl) diazomethane, 1,3-bis (cyclohexylsulfonylazomethylsulfonyl) propane, 1,4 -Bis (phenylsulfonylazomethylsulfonyl) butane, 1,6-bis (phenylsulfonylazomethylsulfonyl) hexane, 1,10-bis (cyclohexylsulfonyla) Bissulfonyldiazomethanes such as methylsulfonyl) decane, 2- (4-methoxyphenyl) -4,6- (bistrichloromethyl) -1,3,5-triazine, 2- (4-methoxynaphthyl) -4,6 Halogen-containing triazine derivatives such as-(bistrichloromethyl) -1,3,5-triazine, tris (2,3-dibromopropyl) -1,3,5-triazine, tris (2,3-dibromopropyl) isocyanurate Etc.

Among the acid generators, the acid generator (C) used in the radiation-sensitive composition of the present embodiment is preferably an acid generator having an aromatic ring, represented by formula (7-1) or (7-2) The acid generator represented by is more preferable. An acid generator having a sulfonate ion having X ^{− in} formula (7-1) or (7-2) having an aryl group or a halogen-substituted aryl group is more preferable, and an acid generator having a sulfonate ion having an aryl group Are particularly preferable, and diphenyltrimethylphenylsulfonium p-toluenesulfonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium trifluoromethanesulfonate, and triphenylsulfonium nonafluoromethanesulfonate are particularly preferable. By using the acid generator, line edge roughness can be reduced.
The acid generator (C) can be used alone or in combination of two or more.

(Acid diffusion control agent (E))
In the radiation-sensitive composition of the present embodiment, an acid having an action of controlling an undesired chemical reaction in an unexposed region by controlling diffusion of an acid generated from an acid generator by irradiation in a resist film. A diffusion control agent (E) may be blended. By using such an acid diffusion controller (E), the storage stability of the radiation-sensitive composition is improved. Further, the resolution is improved, and a change in the line width of the resist pattern due to fluctuations in the holding time before electron beam irradiation and the holding time after electron beam irradiation can be suppressed, and the process stability is extremely excellent. Examples of such an acid diffusion controller (E) include electron beam radiation decomposable basic compounds such as a nitrogen atom-containing basic compound, a basic sulfonium compound, and a basic iodonium compound. The acid diffusion controller can be used alone or in combination of two or more.

  Examples of the acid diffusion controller include nitrogen-containing organic compounds and basic compounds that decompose upon exposure. Examples of the nitrogen-containing organic compound include a compound represented by the following general formula (10) (hereinafter referred to as “nitrogen-containing compound (I)”), a diamino compound having two nitrogen atoms in the same molecule (hereinafter referred to as “nitrogen-containing compound (I)”). , "Nitrogen-containing compound (II)"), polyamino compounds and polymers having 3 or more nitrogen atoms (hereinafter referred to as "nitrogen-containing compound (III)"), amide group-containing compounds, urea compounds, and And nitrogen heterocyclic compounds. In addition, the said acid diffusion control agent may be used individually by 1 type, and may use 2 or more types together.

General formula (10)

In the general formula (10), R ⁶¹ , R ⁶² and R ⁶³ each independently represent a hydrogen atom, a linear, branched or cyclic alkyl group, an aryl group, or an aralkyl group. The alkyl group, aryl group, or aralkyl group may be unsubstituted or substituted with another functional group such as a hydroxyl group. Here, examples of the linear, branched or cyclic alkyl group include those having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms, specifically, methyl group, ethyl group, n- Propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n-pentyl group, neopentyl group, n-hexyl group, texyl group, n-heptyl group, n-octyl group , N-ethylhexyl group, n-nonyl group, n-decyl group and the like. Moreover, as said aryl group, a C6-C12 thing is mentioned, Specifically, a phenyl group, a tolyl group, a xylyl group, a cumenyl group, 1-naphthyl group, etc. are mentioned. Furthermore, examples of the aralkyl group include those having 7 to 19 carbon atoms, preferably 7 to 13 carbon atoms, and specific examples include a benzyl group, an α-methylbenzyl group, a phenethyl group, and a naphthylmethyl group.

  Specific examples of the nitrogen-containing compound (I) include mono- (cyclohexane) such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-dodecylamine, cyclohexylamine and the like. ) Alkylamines; di-n-butylamine, di-n-pentylamine, di-n-hexylamine, di-n-heptylamine, di-n-octylamine, di-n-nonylamine, di-n-decylamine , Methyl-n-dodecylamine, di-n-dodecylmethyl, cyclohexylmethylamine, dicyclohexylamine and the like di (cyclo) alkylamines; triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n- Pentylamine, tri-n-hexylamine, tri-n-heptylamine, -Tri (cyclo) alkylamines such as n-octylamine, tri-n-nonylamine, tri-n-decylamine, dimethyl-n-dodecylamine, di-n-dodecylmethylamine, dicyclohexylmethylamine, tricyclohexylamine; Alkanolamines such as monoethanolamine, diethanolamine, triethanolamine; aniline, N-methylaniline, N, N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, 4-nitroaniline, diphenylamine , Aromatic amines such as triphenylamine and 1-naphthylamine.

  Specific examples of the nitrogen-containing compound (II) include ethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetrakis (2-hydroxypropyl) ethylenediamine, Tetramethylenediamine, hexamethylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylamine, 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-me Ruechiru] benzene, and 1,3-bis [1- (4-aminophenyl) -1-methylethyl] benzene, and the like.

Specific examples of the nitrogen-containing compound (III) include polyethyleneimine, polyallylamine, and a polymer of N- (2-dimethylaminoethyl) acrylamide.
Specific examples of the amide group-containing compound include, for example, formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide, pyrrolidone, N- And methylpyrrolidone.

  Specific examples of the urea compound include urea, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, tri- Examples thereof include n-butylthiourea.

  Specific examples of the nitrogen-containing heterocyclic compound include imidazoles such as imidazole, benzimidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, 2-phenylbenzimidazole; pyridine, 2-methylpyridine. 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, 2-methyl-4-phenylpyridine, nicotine, nicotinic acid, nicotinamide, quinoline, 8-oxyquinoline And pyridines such as acridine; and pyrazine, pyrazole, pyridazine, quinosaline, purine, pyrrolidine, piperidine, morpholine, 4-methylmorpholine, piperazine, 1,4-dimethylpiperazine, 1,4-diazabicyclo [2.2.2. ] Octane etc. It can gel.

  Examples of the basic compound that decomposes upon exposure include a sulfonium compound represented by the following general formula (11-1) and an iodonium compound represented by the following general formula (11-2). Can do.

Formula (11-1)

Formula (11-2)

In the general formulas (11-1) and (11-2), R ⁷¹ , R ⁷² , R ⁷³ , R ⁷⁴ and R ⁷⁵ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or 1 carbon atom. -6 alkoxy groups, hydroxyl groups or halogen atoms. Z ⁻ represents HO ⁻ , R—COO ⁻ (wherein R represents an alkyl group having 1 to 6 carbon atoms, an aryl group having 1 to 6 carbon atoms, or an alkaryl group having 1 to 6 carbon atoms) or the following general formula An anion represented by (11-3) is shown.

(11-3)

  Specific examples of the basic compound that decomposes upon exposure include triphenylsulfonium hydroxide, triphenylsulfonium acetate, triphenylsulfonium salicylate, diphenyl-4-hydroxyphenylsulfonium hydroxide, and diphenyl-4-hydroxyphenyl. Sulfonium acetate, diphenyl-4-hydroxyphenylsulfonium salicylate, bis (4-t-butylphenyl) iodonium hydroxide, bis (4-t-butylphenyl) iodonium acetate, bis (4-t-butylphenyl) iodonium hydro Oxide, bis (4-t-butylphenyl) iodonium acetate, bis (4-t-butylphenyl) iodonium salicylate, 4-t-butylphenyl 4- hydroxyphenyl iodonium hydroxide, 4-t-butylphenyl-4-hydroxyphenyl iodonium acetate, include 4-t-butylphenyl-4-hydroxyphenyl iodonium salicylate and the like.

  The content of the acid diffusion controller (E) is preferably 0.001 to 50 mass%, more preferably 0.001 to 10 mass%, and more preferably 0.001 to 5 mass% of the total solid content in the radiation-sensitive composition. % By mass is more preferable, and 0.001 to 3% by mass is particularly preferable. When the content of the acid diffusion control agent (E) is within the above range, it is possible to prevent deterioration in resolution, pattern shape, dimensional fidelity, and the like. Furthermore, even if the holding time from electron beam irradiation to heating after radiation irradiation becomes longer, the shape of the pattern upper layer portion does not deteriorate. Moreover, a fall of a sensitivity, the developability of an unexposed part, etc. can be prevented as content of an acid diffusion control agent (E) is 10 mass% or less. Further, by using such an acid diffusion control agent, the storage stability of the radiation-sensitive composition is improved, the resolution is improved, and the holding time before irradiation and the holding time after irradiation are reduced. Changes in the line width of the resist pattern due to fluctuations can be suppressed, and the process stability is extremely excellent.

(Other ingredients (F))
In the radiation-sensitive composition of the present embodiment, as long as the purpose of the present invention is not hindered, as other components (F), a dissolution accelerator, a dissolution controller, a sensitizer, and a surfactant are included as necessary. , And various additives such as organic carboxylic acids or phosphorus oxo acids or derivatives thereof may be added.

[1] Dissolution Accelerator A low molecular weight dissolution accelerator increases the solubility of a cyclic compound during development when the solubility of a resist base material in an alkali or other developer is too low, and moderately increases the dissolution rate of a cyclic compound during development. It is a component which has the effect | action to make it use in the range which does not impair the effect of this invention. Examples of the dissolution accelerator include low molecular weight phenolic compounds such as bisphenols and tris (hydroxyphenyl) methane. These dissolution promoters can be used alone or in admixture of two or more. The blending amount of the dissolution accelerator is appropriately adjusted according to the type of the resist base to be used, but is 0 to 100 parts by weight per 100 parts by weight of the resist base (polymer, hereinafter referred to as the polymer compound of the present embodiment). 100 mass parts is preferable, Preferably it is 0-30 mass parts, More preferably, it is 0-10 mass parts, More preferably, it is 0-2 mass parts.

[2] Solubility control agent A solubilization control agent is a component having an action of controlling the solubility of the resist base material when the resist base material is too high in alkali or the like to moderately reduce the dissolution rate during development. It is. As such a dissolution control agent, those that do not chemically change in steps such as baking of resist film, irradiation with radiation, and development are preferable. Examples of the dissolution control agent include aromatic hydrocarbons such as naphthalene, phenanthrene, anthracene, and acenaphthene; ketones such as acetophenone, benzophenone, and phenylnaphthyl ketone; and sulfones such as methylphenylsulfone, diphenylsulfone, and dinaphthylsulfone. Can be mentioned. These dissolution control agents can be used alone or in combination of two or more.
The blending amount of the dissolution controller is appropriately adjusted according to the type of the polymer compound of the present embodiment to be used, but is preferably 0 to 100 parts by weight, preferably 100 parts by weight of the polymer compound of the present embodiment. It is 0-30 mass parts, More preferably, it is 0-10 mass parts, More preferably, it is 0-2 mass parts.

[3] Sensitizer The sensitizer absorbs the energy of the irradiated radiation and transmits the energy to the acid generator (C), thereby increasing the amount of acid generated. It is a component that improves the apparent sensitivity. Examples of such sensitizers include, but are not limited to, benzophenones, biacetyls, pyrenes, phenothiazines, and fluorenes.
These sensitizers can be used alone or in combination of two or more. The blending amount of the sensitizer is appropriately adjusted according to the type of the polymer compound of the present embodiment to be used, but is preferably 0 to 100 parts by weight, preferably 100 parts by weight of the polymer compound of the present embodiment. It is 0-30 mass parts, More preferably, it is 0-10 mass parts, More preferably, it is 0-2 mass parts.

[4] Surfactant A surfactant is a component having an action of improving the coating property and striation of the radiation-sensitive composition of the present invention, the developability of a resist, and the like. Such a surfactant may be anionic, cationic, nonionic or amphoteric. A preferred surfactant is a nonionic surfactant. Nonionic surfactants have better affinity with the solvent used in the production of the radiation-sensitive composition and are more effective. Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers and higher fatty acid diesters of polyethylene glycol, but are not particularly limited. Commercially available products include the following trade names: F-top (manufactured by Gemco), Mega-Fac (manufactured by Dainippon Ink and Chemicals), Florard (manufactured by Sumitomo 3M), Asahi Guard, Surflon (manufactured by Asahi Glass Co., Ltd.), Examples include Pepol (manufactured by Toho Chemical Industry Co., Ltd.), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), polyflow (manufactured by Kyoeisha Yushi Chemical Co., Ltd.), and the like.
The blending amount of the surfactant is appropriately adjusted according to the type of the polymer compound of the present embodiment to be used, but is preferably 0 to 100 parts by weight, preferably 100 parts by weight of the polymer compound of the present embodiment. It is 0-30 mass parts, More preferably, it is 0-10 mass parts, More preferably, it is 0-2 mass parts.

[5] Organic carboxylic acid or phosphorous oxo acid or derivative thereof The radiation-sensitive composition of the present embodiment is further used as an optional component for the purpose of preventing sensitivity deterioration or improving the resist pattern shape, retention stability, etc. Organic carboxylic acids or phosphorus oxo acids or their derivatives can be included. In addition, it can be used in combination with an acid diffusion controller, or may be used alone. As the organic carboxylic acid, for example, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid and the like are suitable. Phosphorus oxoacids or derivatives thereof include phosphoric acid, phosphoric acid di-n-butyl ester, phosphoric acid diphenyl ester and the like, and derivatives such as phosphonic acid, phosphonic acid dimethyl ester, phosphonic acid di- Derivatives such as n-butyl ester, phenylphosphonic acid, phosphonic acid diphenyl ester, phosphonic acid dibenzyl ester, etc., phosphonic acid or their esters, phosphinic acid, phosphinic acid such as phenylphosphinic acid, and derivatives thereof. Of these, phosphonic acid is particularly preferred.
The organic carboxylic acid or phosphorus oxo acid or derivative thereof may be used alone or in combination of two or more. The amount of the organic carboxylic acid or phosphorus oxo acid or derivative thereof is appropriately adjusted according to the type of the polymer compound of the present embodiment to be used, but is 0 to 100 parts by mass of the polymer compound of the present embodiment. 100 mass parts is preferable, Preferably it is 0-30 mass parts, More preferably, it is 0-10 mass parts, More preferably, it is 0-2 mass parts.

[6] The dissolution control agent, the sensitizer, the surfactant, and other additives other than the organic carboxylic acid or the oxo acid of phosphorus or a derivative thereof. One or more additives other than the dissolution control agent, the sensitizer, and the surfactant can be blended as necessary within a range not inhibiting the purpose. Examples of such additives include dyes, pigments, and adhesion aids. For example, it is preferable to add a dye or a pigment because the latent image in the exposed area can be visualized and the influence of halation during exposure can be reduced. In addition, it is preferable to add an adhesion assistant because the adhesion to the substrate can be improved. Furthermore, examples of other additives include an antihalation agent, a storage stabilizer, an antifoaming agent, a shape improving agent, and the like, specifically 4-hydroxy-4′-methylchalcone.

Formulation of the radiation sensitive composition of the present embodiment (polymer compound of the present embodiment / acid generator (C) / acid diffusion controller (E) / other components (F)) is in mass parts based on solid matter. so,
Preferably, 10-90 / 0.001-50 / 0.01-50 / 0-50,
More preferably, 30 to 90 / 0.001 to 50 / 0.01 to 5/0 to 15,
More preferably, 50-80 / 10-37.5 / 0.01-3 / 0-1
Particularly preferred is 70 to 75/10 to 30 / 0.01 to 3/0.
When the elements contained in the radiation-sensitive composition of the present embodiment are formulated as described above, performances such as sensitivity, resolution, and alkali developability can be further improved.

  The radiation-sensitive composition of this embodiment is usually prepared by dissolving each component in a solvent at the time of use to make a uniform solution, and then filtering with a filter having a pore size of about 0.2 μm, if necessary. Is done.

(solvent)
Examples of the solvent used for the preparation of the radiation-sensitive composition of the present embodiment include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, and ethylene glycol mono-n. Ethylene glycol monoalkyl ether acetates such as butyl ether acetate; ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono-n -Propyl ether acetate, propylene glycol mono-n-butyl ether acetate Propylene glycol monoalkyl ether acetates; propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether and propylene glycol monoethyl ether; methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, n-amyl lactate, etc. Lactic acid esters; aliphatic carboxylic acid esters such as methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, n-amyl acetate, n-hexyl acetate, methyl propionate, ethyl propionate; 3-methoxypropion Acid methyl, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxy Other esters such as tilacetate, butyl 3-methoxy-3-methylpropionate, butyl 3-methoxy-3-methylbutyrate, methyl acetoacetate, methyl pyruvate, ethyl pyruvate; aromatic carbonization such as toluene, xylene Hydrogen; ketones such as 2-heptanone, 3-heptanone, 4-heptanone, cyclopentanone, cyclohexanone; N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, etc. Amides; lactones such as γ-lactone can be exemplified, but are not particularly limited. These solvents can be used alone or in combination of two or more.

  Solvents used in the radiation sensitive composition of the present embodiment include propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone (CHN), cyclopentanone (CPN), 2-heptanone, and anisole. A solvent selected from butyl acetate, ethyl propionate, and ethyl lactate can be preferably exemplified. The solvent is a solvent that dissolves the polymer compound of the present embodiment at 23 ° C., preferably 1% by mass or more, more preferably 5% by mass or more, further preferably 10% by mass or more, and particularly preferably 20% by mass or more. Is preferably used. Most preferably, it is preferable to use a solvent selected from PGMEA, PGME, and CHN and exhibiting the highest solubility in the polymer compound of the present embodiment. By using a solvent that satisfies the above conditions, it can be used in a semiconductor manufacturing process in actual production, and storage stability can be improved.

  The radiation-sensitive composition of the present embodiment can contain a resin that is soluble in an alkaline aqueous solution as long as the object of the present invention is not impaired. Resins that are soluble in an aqueous alkaline solution include novolak resins, polyvinylphenols, polyacrylic acid, polyvinyl alcohol, styrene-maleic anhydride resins, and heavy polymers containing acrylic acid, vinyl alcohol, or vinyl phenol as monomer units. A combination, or a derivative thereof may be used. The blending amount of the resin soluble in the alkaline aqueous solution is appropriately adjusted according to the kind of the cyclic compound to be used, but is preferably 0 to 30 parts by mass, more preferably 0 to 10 parts per 100 parts by mass of the cyclic compound. Part by mass, more preferably 0 to 5 parts by mass, particularly preferably 0 part by mass.

[Method of forming resist pattern]
The pattern (resist pattern) forming method of the present embodiment includes a film forming step of forming a film (resist film) on a substrate using the radiation-sensitive composition of the present embodiment, and the film (resist film). And a development step of developing the film (resist film) exposed in the exposure step to form a pattern (resist pattern). The resist pattern obtained by the pattern forming method of the present embodiment can also be formed as an upper layer resist in a multilayer resist process.

  The method for forming a specific pattern is not particularly limited, and examples thereof include the following methods. First, in order to form a resist pattern, a resist film is formed by applying the radiation-sensitive composition of the present embodiment on a conventionally known substrate by a coating means such as spin coating, casting coating, roll coating or the like. To do. The conventionally known substrate is not particularly limited, and examples thereof include a substrate for electronic parts and a substrate on which a predetermined wiring pattern is formed. More specifically, a silicon substrate, a metal substrate such as copper, chromium, iron, and aluminum, a glass substrate, and the like can be given. Examples of the wiring pattern material include copper, aluminum, nickel, and gold. If necessary, an inorganic and / or organic film may be provided on the substrate. An inorganic antireflection film (inorganic BARC) is an example of the inorganic film. Examples of the organic film include an organic antireflection film (organic BARC). Surface treatment with hexamethylene disilazane or the like may be performed.

  Next, the coated substrate is heated as necessary. Although heating conditions change with the compounding composition etc. of a radiation sensitive composition, 20-250 degreeC is preferable, More preferably, it is 20-150 degreeC. Heating may improve the adhesion of the resist to the substrate, which is preferable. Next, the resist film is exposed to a desired pattern with any radiation selected from the group consisting of visible light, ultraviolet light, excimer laser, electron beam, extreme ultraviolet light (EUV), X-ray, and ion beam. The exposure conditions and the like are appropriately selected according to the composition of the radiation sensitive composition. In the present invention, in order to stably form a high-precision fine pattern in exposure, heating is preferably performed after irradiation with radiation. Although heating conditions change with the compounding composition etc. of a radiation sensitive composition, 20-250 degreeC is preferable, More preferably, it is 20-150 degreeC.

  Next, by developing the exposed resist film with an alkaline developer, a predetermined positive resist pattern can be formed. Examples of the alkaline developer include alkaline such as mono-, di- or trialkylamines, mono-, di- or trialkanolamines, heterocyclic amines, tetramethylammonium hydroxide (TMAH), choline and the like. An alkaline aqueous solution in which one or more compounds are dissolved so as to have a concentration of preferably 1 to 10% by mass, more preferably 1 to 5% by mass is used. When the concentration of the alkaline aqueous solution is 10% by mass or less, it is preferable because the exposed portion can be prevented from being dissolved in the developer.

  In addition, an appropriate amount of alcohols such as methanol, ethanol, isopropyl alcohol, and the surfactant can be added to the alkaline developer. Of these, it is particularly preferable to add 10 to 30% by mass of isopropyl alcohol. This is preferable since the wettability of the developer with respect to the resist can be improved. In addition, when using the developing solution which consists of such alkaline aqueous solution, generally it wash | cleans with water after image development.

  On the other hand, a predetermined positive type or negative type resist pattern can be formed by developing the exposed resist film with an organic developer. As the organic developer, a developer containing at least one solvent selected from a ketone solvent, an ester solvent, an alcohol solvent, an amide solvent, and an ether solvent may be used for resist pattern resolution and roughness. It is preferable for improving the resist performance.

  The vapor pressure of the developer is not particularly limited. For example, at 20 ° C., 5 kPa or less is preferable, 3 kPa or less is more preferable, and 2 kPa or less is particularly preferable. By setting the vapor pressure of the developing solution to 5 kPa or less, evaporation of the developing solution on the substrate or in the developing cup is suppressed, temperature uniformity in the wafer surface is improved, and as a result, dimensional uniformity in the wafer surface is improved. It improves.

  Specific examples of the developer having a vapor pressure of 5 kPa or less include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 4-heptanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, Ketone solvents such as methyl isobutyl ketone; butyl 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-ethoxypropionate, 3- Estes such as methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate N-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, 4-methyl-2-pentanol, n-heptyl alcohol, n- Alcohol solvents such as octyl alcohol and n-decanol; glycol solvents such as ethylene glycol, diethylene glycol and triethylene glycol; ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl Glycol ethers such as ether, triethylene glycol monoethyl ether, methoxymethylbutanol Agents: ether solvents such as tetrahydrofuran; amide solvents of N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide; aromatic hydrocarbon solvents such as toluene and xylene; octane, decane Aliphatic hydrocarbon solvents such as

  Specific examples of the developer having a vapor pressure of 2 kPa or less, which is a particularly preferable range, include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 4-heptanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methyl Ketone solvents such as cyclohexanone and phenylacetone; butyl 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-ethoxypropionate, 3 Ester solvents such as methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl lactate, butyl lactate and propyl lactate; n-butyl alcohol , Sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, 4-methyl-2-pentanol, n-heptyl alcohol, n-octyl alcohol, n-decanol and other alcohol solvents; ethylene glycol, Glycol solvents such as diethylene glycol and triethylene glycol; glycols such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methoxymethyl butanol Ether solvents; N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethyl Le formamide amide solvent; aromatic hydrocarbon solvents such as xylene, octane, include aliphatic hydrocarbon solvents decane.

  An appropriate amount of a surfactant can be added to the developer as necessary. The surfactant is not particularly limited, and for example, ionic or nonionic fluorine-based and / or silicon-based surfactants can be used. Examples of these fluorine and / or silicon surfactants are, for example, JP-A-62-36663, JP-A-61-226746, JP-A-61-226745, JP-A-62-170950. JP-A-63-34540, JP-A-7-230165, JP-A-8-62834, JP-A-9-54432, JP-A-9-5988, US Pat. No. 5,405,720, Mention may be made of the surfactants described in US Pat. Nos. 5,360,692, 5,529,881, 5,296,330, 5,436,098, 5,576,143, 5,294,511, and 5,824,451. Preferably, it is a nonionic surfactant. Although it does not specifically limit as a nonionic surfactant, It is more preferable to use a fluorochemical surfactant or a silicon-type surfactant.

  The amount of the surfactant used is usually about 0.001 to 5% by mass, preferably 0.005 to 2% by mass, more preferably 0.01 to 0.5% by mass, based on the total amount of the developer. is there.

  As a developing method, for example, a method in which a substrate is immersed in a tank filled with a developer for a certain period of time (dip method), a method in which the developer is raised on the surface of the substrate by surface tension and is left stationary for a certain time (paddle) Method), a method of spraying the developer on the substrate surface (spray method), a method of continuously applying the developer while scanning the developer application nozzle at a constant speed on a substrate rotating at a constant speed (dynamic dispensing method) ) Etc. can be applied. The time for developing the pattern is not particularly limited, but is preferably 10 seconds to 90 seconds.

Moreover, you may implement the process of stopping image development, substituting with another solvent after a image development process.
Furthermore, after the development step, a step of washing with a rinse solution containing an organic solvent can be included. The rinsing liquid used in the rinsing step after development is not particularly limited as long as the resist pattern cured by crosslinking is not dissolved, and a solution or water containing a general organic solvent can be used. As the rinsing liquid, it is preferable to use a rinsing liquid containing at least one organic solvent selected from hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents. . More preferably, after the development, a cleaning step is performed using a rinse solution containing at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, and amide solvents. More preferably, after the development, a cleaning step is performed using a rinse solution containing an alcohol solvent or an ester solvent. Even more preferably, after the development, a step of washing with a rinsing solution containing a monohydric alcohol is performed. Particularly preferably, after the development, a washing step is performed using a rinsing liquid containing a monohydric alcohol having 5 or more carbon atoms. The time for rinsing the pattern is not particularly limited, but is preferably 10 seconds to 90 seconds.

  Here, the monohydric alcohol used in the rinsing step after development is not particularly limited, and examples thereof include linear, branched, and cyclic monohydric alcohols. Specifically, 1-butanol, 2 -Butanol, 3-methyl-1-butanol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 1-hexanol, 4-methyl-2-pentanol, 1-heptanol, 1-octanol, 2-hexanol , Cyclopentanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol and the like, and particularly preferable monohydric alcohols having 5 or more carbon atoms include 1-hexanol, 2-hexanol, 4-methyl-2-pentanol, 1-pentanol, 3-methyl And 1-butanol.

  A plurality of the above components may be mixed, or may be used by mixing with an organic solvent other than the above.

  The moisture content in the rinse liquid is not particularly limited, but is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 3% by mass or less. By setting the water content to 10% by mass or less, better development characteristics can be obtained.

  The vapor pressure of the rinsing solution used after development is preferably 0.05 kPa or more and 5 kPa or less, more preferably 0.1 kPa or more and 5 kPa or less, and further preferably 0.12 kPa or more and 3 kPa or less at 20 ° C. By setting the vapor pressure of the rinsing liquid to 0.05 kPa or more and 5 kPa or less, the temperature uniformity in the wafer surface is further improved, and further, the swelling due to the penetration of the rinsing liquid is further suppressed, and the dimensions in the wafer surface are reduced. Uniformity is improved.

  An appropriate amount of a surfactant can be added to the rinse solution.

  In the rinsing step, the developed wafer is cleaned using a rinsing solution containing the organic solvent. The method of the cleaning treatment is not particularly limited. For example, a method of continuously applying a rinse liquid onto a substrate rotating at a constant speed (rotary coating method), or immersing the substrate in a tank filled with the rinse liquid for a certain period of time. A method (dip method), a method of spraying a rinsing liquid on the substrate surface (spray method), and the like can be applied. Among them, a cleaning treatment is performed by a spin coating method, and after cleaning, the substrate is rotated at a speed of 2000 rpm to 4000 rpm. It is preferable to rotate and remove the rinse liquid from the substrate.

After forming the resist pattern, the pattern wiring board is obtained by etching. The etching can be performed by a known method such as dry etching using plasma gas and wet etching using an alkali solution, a cupric chloride solution, a ferric chloride solution, or the like.
Plating can be performed after forming the resist pattern. Examples of the plating method include copper plating, solder plating, nickel plating, and gold plating.
The residual resist pattern after etching can be peeled off with an organic solvent or a stronger alkaline aqueous solution than the alkaline aqueous solution used for development. Examples of the organic solvent include PGMEA (propylene glycol monomethyl ether acetate), PGME (propylene glycol monomethyl ether), EL (ethyl lactate) and the like. As the strong alkaline aqueous solution, for example, 1 to 20% by mass of sodium hydroxide aqueous solution or 1-20 mass% potassium hydroxide aqueous solution is mentioned. Examples of the peeling method include a dipping method and a spray method. Further, the wiring board on which the resist pattern is formed may be a multilayer wiring board or may have a small diameter through hole.
The wiring board obtained by the present invention can also be formed by a method of depositing a metal in vacuum after forming a resist pattern and then dissolving the resist pattern with a solution, that is, a lift-off method.

  Hereinafter, the embodiment of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.

[Example 1]
-Synthesis of Poly (tBCRA [4] -co-ADB)-
Using a 200 ml eggplant flask, 1.02 g (1.0 mmol) of Ct-butylphenyl [4] calixresorcinarene (hereinafter referred to as “tBCRA [4]”) was dissolved in 20 ml of N-methylpyrrolidone. . Next, 0.8 g (0.25 mmol) of tetrabutylammonium bromide and 0.288 g (12 mmol) of sodium hydride were added and stirred at 80 ° C. for 2 hours. Thereafter, 1.63 g (4.0 mmol) of bromoacetic acid-2-methyladamantan-2-yl was added and reacted under conditions of 80 ° C. for 48 hours. After completion of the reaction, reprecipitation was performed with a 1N HCl aqueous solution, followed by filtration, and then washing with water to obtain a solid. The resulting solid was then dissolved in ethyl acetate and purified by column chromatography. The structure of the obtained solid (compound) was confirmed by ¹ H-NMR (Nuclear Magnetic Resonance) and IR (Infrared Absorption Spectrometry). 1 is a diagram showing a ¹ H-NMR spectrum of the compound synthesized in Synthesis Example 1. FIG. FIG. 2 is a diagram showing an IR spectrum of the compound obtained in Synthesis Example 1.
As a result of confirming the structure, the obtained compound was obtained in the above general formula (1) where R ¹ is hydrogen, R ² is a linking group derived from bromoacetate-2-methyladamantan-2-yl, and R ³ is a t-butylphenyl group. M ₁ + n ₁ = m ₂ + n ₂ = 4 (Ct-butylphenyl [4] calixresorcinarene and bromoacetate-2-methyladamantan-2-yl condensation reaction product (hereinafter referred to as “ Poly (tBCRA [4] -co-ADB) "))). Moreover, it confirmed that the following compound was contained in the mixture. Poly (tBCRA [4] -co-ADB) has a tetramer structure as described below.

Poly (tBCRA [4] -co-ADB)

The number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) of the obtained solid (compound) were calculated by SEC (Size Exclusion Chromatography) measurement using dimethylformamide as an eluent. The introduction rate of adamantane relative to the compound was calculated from the integrated intensity ratio of the signal attributed to the aromatic proton of tBCRA [4] of ¹ H-NMR and the signal attributed to the proton of the adamantyl ester.

  From the measurement results, Poly (tBCRA [4] -co-ADB) has a yield of 1.1 g, a yield of 49%, Mn = 3360 (Mw / Mn = 1.54), and a reaction rate of the hydroxyl group of tBCRA [4]. = 70%, Tdi = 216 ° C, Td 5% (5 mass% heat loss temperature) = 280 ° C.

[Example 2]
-Synthesis of Poly (CCRA [4] -co-ADB)-
tBCRA [4] was changed to 4-C-cyclohexylphenyl [4] calixresorcinarene (hereinafter referred to as “CCRA [4]”), and others were carried out in the same manner as in Example 1, except that the above general formula ( In 1), R ¹ is hydrogen, R ² is a linking group derived from bromoacetate-2-methyladamantan-2-yl, R ³ is a 4-C-cyclohexylphenyl group, m ₁ + n ₁ = m ₂ + n ₂ = 4, A compound (4-C-cyclohexylphenyl [4] calixresorcinarene and a condensation reaction product of bromoacetate-2-methyladamantan-2-yl (hereinafter referred to as “Poly (CCRA [4] -co-ADB)”) It was confirmed that a mixture was obtained. Moreover, it confirmed that the following compound was contained in the mixture. Poly (CCRA [4] -co-ADB) has a tetramer structure as follows.

Poly (CCRA [4] -co-ADB)

[Example 3]
-Synthesis of Poly (iPCRA [4] -co-ADB)-
tBCRA [4] was changed to 4-C-i-propylphenyl [4] calixresorcinarene (hereinafter referred to as “iPCRA [4]”), and others were performed in the same manner as in Example 1, In formula (1), R ¹ is hydrogen, R ² is a linking group derived from bromoacetate-2-methyladamantan-2-yl, R ³ is a 4-C-i-propylphenyl group, m ₁ + n ₁ = m ₂ + n ₂ = 4, a compound (4-Ci-propylphenyl [4] calixresorcinarene and a condensation reaction product of bromoacetate-2-methyladamantan-2-yl (hereinafter referred to as “Poly (iPCRA [4] − co-ADB) ”))) was confirmed to be obtained. Moreover, it confirmed that the following compound was contained in the mixture. Poly (iPCRA [4] -co-ADB) has a tetramer structure as described below.

Poly (iPCRA [4] -co-ADB)

[Example 4]
-Synthesis of Poly (BCRA [4] -co-mXG)-
Bromoacetic acid-2-methyladamantan-2-yl was changed to 1,3-bis [(chloromethoxy) methyl] benzene (hereinafter referred to as “mXG”), and others were carried out in the same manner as in Example 1, and the above-mentioned In general formula (1), R ¹ is hydrogen, R ² is a linking group derived from 1,3-bis [(chloromethoxy) methyl] benzene, R ³ is a t-butylphenyl group, m ₁ + n ₁ = m ₂ + n ₂ = 4, a compound (4-t-butylphenylcalix [4] arene and 1,3-bis [(chloromethoxy) methyl] benzene condensation reaction product (hereinafter referred to as “Poly (BCRA [4] -co -MXG "))) was obtained, and the mixture was confirmed to contain the following compound: Poly (BCRA [4] -co-mXG) It has a tetramer structure as shown below .

Poly (BCRA [4] -co-mXG)

<Preparation and evaluation of radiation-sensitive composition>
[Patterning test]
The components listed in Table 1 below were prepared to make a uniform solution. Then, it filtered with the membrane filter made from a Teflon (trademark) with a hole diameter of 0.1 micrometer, and prepared the radiation sensitive composition. The following evaluation was performed about the obtained radiation sensitive composition. The results are shown in Table 2.

(1) Evaluation of sensitivity A radiation-sensitive composition (resist) was spin-coated on a clean silicon wafer and then prebake in an oven to form a resist film having a thickness of 60 nm. Using an electron beam drawing apparatus (manufactured by Elionix Co., Ltd., product name: ELS-7500), the obtained resist film was irradiated with an electron beam with a line and space setting of 1: 1 at 100 nm intervals. After irradiation with the electron beam, the resist film was heated at a predetermined temperature (PEB shown in Table 2 below) for 90 seconds and developed with THF for 60 seconds. Then, it dried and formed the resist pattern. The line and space of the obtained resist pattern was observed with a scanning electron microscope (product name: S-4800, manufactured by Hitachi High-Technology Co., Ltd.), and was obtained according to the following evaluation criteria based on the dose (μC / cm ² ). The sensitivity of the polymer compound was evaluated.
[Evaluation criteria]
A: Dose amount ≦ 30 μC / cm ² (excellent sensitivity)
B: 30 μC / cm ² <dose amount ≦ 800 μC / cm ² (good sensitivity)
C: 800 μC / cm ² <Dose amount (poor sensitivity)

(2) Evaluation of Line Edge Roughness (LER) A resist pattern was produced with a 1: 1 line and space setting at 100 nm intervals by the same method as in the evaluation of (1). At arbitrary 300 points in the length direction (0.75 μm) of 1: 1 line and space at 100 nm intervals, using SEM terminal PC V5 offline length measurement software (manufactured by Hitachi Science Systems, Ltd.) for Hitachi Semiconductor, The distance between the edge and the reference line was measured. A standard deviation (3σ) was calculated from the measurement results, and the LER of the pattern was evaluated according to the following evaluation criteria.
[Evaluation criteria]
A: LER (3σ) ≦ 3.5 nm (good LER)
C: 3.5 nm <LER (3σ) (not good LER)

(3) Pattern collapse evaluation A 1: 1 line-and-space resist pattern with an interval of 30 nm was formed in an area of 1 μm square by the same method as in (1) Evaluation of sensitivity. The obtained line and space was observed with a scanning electron microscope (manufactured by Hitachi High-Technology Corporation, product name: S-4800), and pattern collapse was evaluated according to the following evaluation criteria.
[Evaluation criteria]
A: No pattern collapse C: Some pattern collapse

  From the results of the patterning test described above, it was confirmed that the radiation-sensitive composition using the polymer compound of the present embodiment has good sensitivity and LER and can suppress collapse in a fine pattern.

In Table 1, the acid generator, the acid diffusion controller and the solvent are as follows.
(Acid generator)
P-1: Triphenylbenzenesulfonium trifluoromethanesulfonate (Midori Chemical Co., Ltd.)
(Acid diffusion control agent)
Q-1: Trioctylamine (Tokyo Chemical Industry Co., Ltd.)
(solvent)
S-1: Propylene glycol monomethyl ether (Tokyo Chemical Industry Co., Ltd.)

PEB: Temperature when heating after electron beam irradiation

  The polymer compound of the present invention can be suitably used for, for example, an acid amplification type radiation sensitive composition and a resist pattern forming method using the composition.

Claims (5)

The high molecular compound containing the unit structure shown by following General formula (1).
General formula (1)
(In the general formula (1), m ₁ is an integer of ₁ to 8, n ₁ is an integer of 0 to 7, m ₁ + n ₁ = an integer of 4 to 8, and m ₂ is 1 to 8. N ₂ is an integer of 0 to 7, m ₂ + n ₂ = an integer of 4 to 8, y is independently an integer of 0 to 2, and R ¹ is independently a hydroxyl group A substituted or unsubstituted linear group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, Alternatively, a halogen atom, R ³ each independently represent a hydrogen atom, a substituted or unsubstituted straight, cyclic alkyl, branched or C3-20 having 3 to 20 carbon atoms group one, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, indicated R ² are each independently the following general formula (2) It is a structure of However, .R ⁵ having at least one R ² is an acid dissociable portion, ^{hydroxyl, -O-R 2 -O -.} *, (* Indicates the binding site between the unit structure.) Or —O—R ² —O—R ⁵⁵ (R ⁵⁵ is other R ⁵ in the general formula (1)), and R ⁶ is a hydroxyl group or —O—R ² —O— *. Yes (* indicates a binding site between the unit structures)
General formula (2)
(In the general formula (2), R ⁴ is a substituted or unsubstituted C 1-20 linear, C 3-20 branched or C 3-20 cyclic alkylene group, or It is a substituted or unsubstituted arylene group having 6 to 20 carbon atoms.) In the general formula (1), R ³ is a substituted or unsubstituted linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 3 to 20 carbon atoms, The polymer compound according to claim 1, which is an unsubstituted aryl group having 6 to 10 carbon atoms.   A radiation-sensitive composition comprising the polymer compound according to claim 1.   Furthermore, the radiation sensitive composition of Claim 3 containing a solvent. A film forming step of forming a film on a substrate using the radiation-sensitive composition according to claim 3 or 4,
An exposure step of exposing the film;
A development step of developing the film exposed in the exposure step to form a pattern.