WO2005105873A1 - Resin for resist composition, negative resist composition and method for forming resist pattern - Google Patents

Abstract

A resin for a resist composition, which comprises a constituting unit (a1) containing an alicyclic group having a fluorinated hydroxyalkyl group, and a constituting unit (a2) being derived from an acrylic acid ester and containing a hydroxyl group-containing alicyclic group; and a negative resist composition which comprises the above resin for a resist composition. A resist pattern is formed by the use of the negative resist composition.

Description

 Specification

 Resin for resist composition, negative resist composition and method for forming resist pattern

 Technical field

 The present invention relates to a resin for a resist composition, a negative resist composition, and a method for forming a resist pattern.

 Priority is claimed on Japanese Patent Application No. 2004-131115 filed on Apr. 27, 2004 and Japanese Patent Application No. 2004-263375, filed on Sep. 10, 2004 with the Japan Patent Office. The contents are incorporated herein.

 Background art

 [0002] Conventionally, negative resist compositions used in processes using i-line or KrF excimer laser light (248 nm) as light sources include acid generators and alkali-soluble resins such as novolak resins and polyhydroxystyrene. A chemically amplified negative resist containing a combination of an amino resin such as a melamine resin and a urea resin is used (for example, Patent Document 1).

 [0003] Further, as a negative resist composition applicable to a process using an ArF excimer laser having a shorter wavelength, a resin composition having improved transparency to an ArF excimer laser, for example, a resin component having a carboxyl group, an alcohol, Negative resist compositions containing a crosslinking agent having a hydrophilic hydroxyl group and an acid generator have been proposed.

 This is a type in which the carboxyl group of the resin component reacts with the alcoholic hydroxyl group of the crosslinking agent by the action of an acid which also generates an acid generator, thereby changing the resin component from alkali-soluble to insoluble.

A negative resist composition containing a resin component having a carboxyl group or a carboxylic acid ester group and an alcoholic hydroxyl group, respectively, and an acid generator, wherein a carboxyl group or a carboxylic acid ester group in the resin component is contained. A type in which the fatty acid component is changed to insoluble by dissolving the fatty acid component into alkali by reacting the alcohol component with an alcoholic hydroxyl group by the action of an acid generated from an acid generator (for example, Non-patent documents 1-3, patent document 2, etc.). Patent Document 1: Japanese Patent Publication No. 8-3635

 Patent Document 2: Japanese Patent Application Laid-Open No. 2000-206694

 Non Patent Literature 1: Journal of Photopolymer Science and Technology (J. Photopolym. Sci. Tech.), Vol. 10, No. 4, pp. 579-584 (1997) : Job Photopolym. Sci. Tech., Vol. 11, No. 3, pp. 507-512 (1998) Non-Patent Literature 3: SPIE Advances in Resist Technology and Processing XIV, Vol. 333J, p417-424 (1998)

 Non-Patent Document 4: SPIE Advances in Resist technology and Processing XIX, Vol. 4690, p94-100 (2002)

 Disclosure of the invention

 Problems to be solved by the invention

[0004] However, in the case of a negative resist composition developed for a conventional ArF excimer laser, there is a problem that the swelling of the resist pattern cannot be sufficiently suppressed even in terms of V and deviation. The swelling of the resist pattern is a very important problem in a process for forming a fine pattern such as using a KrF excimer laser or an ArF excimer laser.

 The present invention has been made in view of the above circumstances, and has as its object to provide a technique capable of suppressing swelling of a resist pattern.

 Means for solving the problem

[0006] In order to achieve the above object, the present invention employs the following configurations.

 The first aspect (aspect) of the present invention is a structural unit (al) containing an alicyclic group having a fluorinated hydroxyalkyl group, and a structural unit derived from an acrylate ester, wherein a hydroxyl group And a structural unit (a2) containing an alicyclic group.

[0007] A second aspect (aspect) of the present invention comprises (A) the resin for a resist composition according to the first aspect of the present invention, (B) an acid generator component which generates an acid upon exposure, and (C) ) It is a negative resist composition containing a crosslinking agent component. [0008] A third aspect of the present invention (aspect) is to apply the negative resist composition of the second aspect of the present invention onto a substrate, pre-beta, and selectively expose, and then perform PEB (post-exposure heating). ), And alkali-developed to form a resist pattern.

[0009] The "structural unit" refers to a monomer unit constituting a polymer (resin).

 "Acrylic acid force-derived structural unit" means a structural unit formed by cleavage of an ethylenic double bond of acrylic acid.

 The “structural unit derived from an acrylate ester” means a structural unit formed by cleavage of an ethylenic double bond of an acrylate ester.

 The “acrylic acid ester derived structural unit” is a concept including a compound in which a hydrogen atom at the α-position is substituted with another substituent such as an alkyl group. In the “structural unit derived from acrylic acid” and the “structural unit derived from acrylate ester”, the term “carbon atom at the α-position” refers to a carboxyl group unless otherwise specified. Is the carbon atom to which is bound.

 The “structural unit from which acrylic acid power is also derived” is a structural unit in which the hydrogen atom bonded to the α-position carbon atom is replaced by another substituent such as an alkyl group, or a hydrogen atom is substituted for the oc-position carbon atom. In addition, in the claims or the specification, the term "alkyl group" refers to a linear group unless otherwise specified. , A cyclic or branched alkyl group.

 “Exposure” is a concept that encompasses not only irradiation of light but also irradiation of radiation such as electron beam irradiation.

 The invention's effect

 In the present invention, a technique capable of suppressing swelling of a resist pattern can be provided.

 BEST MODE FOR CARRYING OUT THE INVENTION

[Resin for resist composition]

The resin for a resist composition of the present invention comprises a structural unit (al) containing an alicyclic group having a fluorinated hydroxyalkyl group and a structural unit derived from an acrylate ester. And a structural unit (a2) containing a hydroxyl group-containing alicyclic group.

First, the structural unit (al) containing an alicyclic group having a fluorinated hydroxyalkyl group will be described.

 In the resin for a resist composition of the present invention, by having the structural unit (al), the effect of suppressing swelling is improved.

[0013] · Alicyclic group having fluorinated hydroxyalkyl group

 In the structural unit (al), the alicyclic group has a fluorinated hydroxyalkyl group. The fluorinated hydroxyalkyl group is different from the alkyl group having a hydroxy group in that a part of hydrogen atoms of the alkyl group Or, all are substituted by fluorine. In such a group, the hydrogen atom of the hydroxyl group is easily released by fluorination.

 With respect to the fluorinated hydroxyalkyl group, the alkyl group is linear or branched, and the number of carbon atoms is not particularly limited, but is, for example, 1 to 20, preferably 4 to 16. The number of hydroxyl groups is not particularly limited, but is usually one.

 Above all, in the alkyl group, a fluorinated alkyl group or a fluorine atom is bonded to the α-position carbon atom to which the hydroxy group is bonded (here, refers to the α-position carbon atom of the hydroxyalkyl group). It is preferable that the fluorinated alkyl group and the fluorine atom are bonded to each other. The fluorinated alkyl group bonded to the α-position is preferably one in which all of the hydrogen atoms of the alkyl group are substituted with fluorine.

 [0014] The alicyclic group may be monocyclic or polycyclic! /, But is preferably a polycyclic group. Further, an alicyclic hydrocarbon group is preferred. Further, it is preferably saturated. Also, the alicyclic group preferably has 5 to 15 carbon atoms! / ,.

 [0015] Specific examples of the alicyclic group include the following.

That is, examples of the monocyclic group include groups in which one hydrogen atom has been removed from a cycloalkane. Examples of the polycyclic group include groups in which one or two hydrogen atoms have been removed from bicycloalkane, tricycloalkane, tetracycloalkane, and the like. And, more specifically, as the monocyclic group, cyclopentane, cyclohexane

Examples include groups in which one or two hydrogen atoms have been removed, and it is preferred that two hydrogen atoms have been removed from cyclohexane.

 Examples of the polycyclic group include groups in which one or two hydrogen atoms have been removed from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.

 A large number of such polycyclic groups have been proposed as constituents of an acid dissociable, dissolution inhibiting group in, for example, a resin for a positive photoresist composition for an ArF excimer laser process! The force can be appropriately selected and used.

 Of these, groups obtained by removing two hydrogen atoms from cyclohexane, adamantane, norbornane, and tetracyclododecane are industrially easily available and are preferred.

 Among these monocyclic and polycyclic groups, a group obtained by removing two hydrogen atoms from norbornane is particularly preferable.

[0016] The structural unit (al) is preferably a structural unit derived from acrylic acid, and the alicyclic group is bonded to an ester group [—c (o) o—] of an atalylic acid ester. Preferred is a structure (a structure in which a hydrogen atom of a carboxyl group is substituted with the alicyclic group).

As the structural unit (al), more specifically, a unit represented by the following general formula (1) is preferable.

[0018] [Formula 1]

• (1)

(In the formula, R is a hydrogen atom, an alkyl group, a fluorinated alkyl group, or a fluorine atom, and m, n, and p are each independently an integer of 1 to 5.)

[0019] R is a hydrogen atom, an alkyl group, a fluorinated alkyl group, or a fluorine atom.

 As the alkyl group, a lower alkyl group having 5 or less carbon atoms is preferable, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group. And the like, and a methyl group is preferred.

 The fluorinated alkyl group is preferably a group in which one or more hydrogen atoms of a lower alkyl group having 5 or less carbon atoms are substituted with a fluorine atom. Specific examples of the alkyl group are the same as those described above.

 The hydrogen atom substituted with a fluorine atom may be a part of the hydrogen atoms constituting the alkyl group or all of them.

 In R, a hydrogen atom or an alkyl group is preferred, a hydrogen atom or a methyl group is particularly preferred, and a hydrogen atom is most preferred.

 Further, n, m, and p are each preferably 1.

[0020] Among the compounds represented by the general formula (1), α, α'bis (trifluoromethyl) bis [2.2.1] hepter 5 ene-2 ethanol acrylate (see the following [I-Dai 7]) The structural units derived from the monomers shown) are effective, easy to synthesize, and have high etching resistance. It is also preferable from the point that the property can be obtained.

The structural unit (al) can be used alone or as a mixture of two or more.

Next, a structural unit (a2) derived from an acrylate ester and containing a hydroxyl group-containing alicyclic group will be described.

In the resin for resist compositions of the present invention, the effect of suppressing swelling is improved by including the structural unit ( _a2 ). Further, the effect of improving the etching resistance can be obtained.

 When the resin for a resist composition of the present invention is blended into a negative resist composition, the hydroxyl group (alcoholic hydroxyl group) iS (B) of the constituent unit (a2) is acted upon by the action of the acid generated from the acid generator to produce ( C) Reacts with the cross-linking agent, whereby the resin for resist composition changes into a property of being soluble in an alkali developer to a property of being insoluble.

[0023] In the structural unit (a2), the hydroxyl group-containing alicyclic group is preferably bonded to an ester group (-C (O) O-) of an acrylate ester.

In the structural unit (a2), another substituent may be bonded to the α-position (the carbon atom at the α-position) instead of a hydrogen atom. The substituent preferably includes an alkyl group, a fluorinated alkyl group, and a fluorine atom.

 These descriptions are the same as the description of R in the general formula (1) of the structural unit (al). (Of those capable of bonding at the X position, preferred is a hydrogen atom or an alkyl group, A hydrogen atom or a methyl group is preferred, and most preferably U is a hydrogen atom.

[0025] The hydroxyl group-containing alicyclic group is a group in which a hydroxyl group is bonded to an alicyclic group.

 The number of hydroxyl groups is preferably, for example, one to three, more preferably one. Further, an alkyl group having 1 to 4 carbon atoms may be bonded to the alicyclic group.

Here, the alicyclic group may be monocyclic or polycyclic! /, But is preferably a polycyclic group. Also

And an alicyclic hydrocarbon group. Further, it is preferably saturated. The alicyclic group preferably has 5 to 15 carbon atoms.

[0027] Specific examples of the alicyclic group include the following.

That is, examples of the monocyclic group include groups in which one hydrogen atom has been removed from a cycloalkane. Examples of the polycyclic group include groups obtained by removing one hydrogen atom from bicycloalkane, tricycloalkane, tetracycloalkane, and the like. And, more specifically, as the monocyclic group, cyclopentane, cyclohexane

A group excluding one hydrogen atom is preferred, and a cyclohexyl group is preferred.

 Examples of polycyclic groups include groups in which one hydrogen atom has been removed from polycycloalkanes such as adamantan, norbornane, isobornane, tricyclodecane, and tetracyclododecane.

 A large number of such polycyclic groups have been proposed as constituents of an acid dissociable, dissolution inhibiting group in, for example, a resin for a positive photoresist composition for an ArF excimer laser process! The force can be appropriately selected and used.

 Among these, a cyclohexyl group, an adamantyl group, a norbornyl group, and a tetracyclododele group are industrially available and readily preferred.

 Among these exemplified monocyclic and polycyclic groups, a cyclohexyl group and an adamantyl group are preferred, and an adamantyl group is particularly preferred.

As a specific example of the structural unit (a2), for example, a structural unit represented by the following general formula (2) is preferable.

[0029] [Formula 2]

(R is a hydrogen atom, an alkyl group, a fluorinated alkyl group or a fluorine atom, and q is an integer of 1-3.)

 R is a hydrogen atom, an alkyl group, a fluorinated alkyl group, or a fluorine atom bonded to the α-position, and is the same as described in the general formula (1). In the general formula (2), R is most preferably a hydrogen atom! / ,.

Also, q is preferably a force 1 which is an integer of 1 to 3. The bonding position of the hydroxyl group is not particularly limited, but is preferably bonded to the 3-position of the adamantyl group.

The structural unit (a2) can be used alone or as a mixture of two or more.

[0032] Next, also induced acrylate force, and a structural unit having no cyclic structure, the structural unit having an alcoholic hydroxyl group in the side chain _(a 3) is described Te Nitsuヽ. In the resin for a resist composition of the present invention, in addition to the structural unit (al) and the structural unit (a2), a structural unit derived from acrylic acid and having no cyclic structure, and having an alcohol in a side chain. It preferably has a structural unit (a3) having a hydroxyl group.

 By having such a structural unit (a3), an effect of improving resolution can be obtained. In addition, film loss can be suppressed. Further, the controllability of the crosslinking reaction at the time of pattern formation is improved. Furthermore, the film density tends to increase. Thereby, the heat resistance tends to be improved. Further, the etching resistance is improved.

 [0033] The expression "has no cyclic structure! /" Means "having no alicyclic group or aromatic group!".

 The structural unit (a3) is clearly distinguished from the structural unit (a2) by not having a cyclic structure. When the resin for a resist composition having the structural unit (a3) is blended into a negative resist composition, the hydroxyl group of the structural unit (a3) and the hydroxyl group of the hydroxyalkyl group of the structural unit (a3) are changed to ( The action of the acid generated from the acid generator (B) reacts with the cross-linking agent (C), whereby the resin for resist composition changes to a property soluble in an alkali developer to a property insoluble in an alkali developer.

 [0034] The phrase "having an alcoholic hydroxyl group in the side chain" includes, for example, structural units having a hydroxyalkyl group bonded thereto.

 The hydroxyalkyl group may be bonded, for example, to the α-position carbon atom of the main chain (the portion where the ethylenic double bond of acrylic acid is cleaved), or may be substituted with a hydrogen atom of the carboxyl group of acrylic acid. In the structural unit (a3) which may form an ester, it is preferable that at least one of these is present and both are present.

When a hydroxyalkyl group is not bonded to the α-position, an alkyl group, a fluorinated alkyl group, or a fluorine atom may be bonded to the carbon atom at the α-position instead of a hydrogen atom. . These are the same as described for R in the general formula (1). The structural unit (a3) is preferably represented by the following general formula (3).

[0037] [Formula 3]

(In the formula, R ¹ is a hydrogen atom, an alkyl group, fluorinated alkyl group, a fluorine atom or a hydroxy Shiarukiru group, R ² represents a hydrogen atom, an alkyl group or hydroxyalkyl group der, is, and, the R ² At least one is a hydroxyalkyl group.)

In [0038] R ^1, hydroxyalkyl group, preferably a lower hydroxyalkyl group of not more than 10 carbon atoms, more preferably a lower hydroxyalkyl group having 2 to 8 carbon atoms, and most preferably a hydroxymethyl group, or It is a hydroxyethyl group. The number and the bonding position of the hydroxyl group are not particularly limited, but are usually one, and it is preferable that the hydroxyl group is bonded to the terminal of the alkyl group.

In R ^1, the alkyl group is preferably a lower alkyl group of not more than 10 carbon atoms, more preferably a lower alkyl group having 2 to 8 carbon atoms, most preferably Echiru group, a methylation group.

In R ^1, the fluorinated alkyl group is preferably a carbon number of 5 or less lower alkyl group (preferably Echiru group, a methyl group) in which part or all of the hydrogen atoms are substituted with fluorine groups.

In R ^2, an alkyl group, hydroxyalkyl group, are similar to those for R ^1.

As the structural unit (a3), specifically, a structural unit derived from α- (hydroxyalkyl) acrylic acid, a structural unit derived from a- (hydroxyalkyl) acrylic acid, and ( (α-alkyl) acrylic acid hydroxyalkyl ester power Structural unit derived.

Above all, the structural unit (a3) is a-(hydro) from the viewpoint of improving the effect and improving the film density. It is preferable to include a constitutional unit derived from an (xyalkyl) alkyl acrylate ester. And, among them, a (hydroxymethyl) acrylate ester or α (hydroxymethyl) -acrylate is also preferred.

Further, it is preferable to include a structural unit derived from the structural unit (a3) hydroxyalkyl (acrylate). Of these, a structural unit derived from a-methyl-acrylic acid hydroxyethyl ester or _α -methyl-acrylic acid hydroxymethyl ester is preferable.

[0040] The structural unit (a3) can be used alone or in combination of two or more.

Next, the structural unit (a4) derived from an acrylate ester containing a rataton-containing monocyclic or polycyclic group will be described.

In the resin for a resist composition of the present invention, in addition to the structural unit (al) and the structural unit ( _a2 ), the resin is derived from an acrylic acid ester containing a monocyclic or polycyclic group containing ratatotone. U, which preferably has the structural unit (a4)

 Further, in the resin for resist composition of the present invention, the structural unit (al), the structural unit (a2)

In addition to the structural unit (a4), the structural unit (a3) may be used in combination.

When used for forming a resist film, the rataton-containing monocyclic or polycyclic group of the structural unit (a4) enhances the adhesion of the resist film to the substrate or increases the hydrophilicity with the developer. It is effective because it can be raised. In addition, the effect of suppressing swelling is improved.

[0043] Note that rataton here refers to one ring including a -O-C (O)-structure, which is counted as one eye ring. Therefore, when only a rataton ring is used, it is called a monocyclic group, and when it has another ring structure, it is called a polycyclic group regardless of its structure.

The structural unit (a4) is not particularly limited as long as it has a rataton ring having both the ester structure (—O—C (O) —) and a ring structure. Can be used

[0045] Specifically, examples of the ratatone-containing monocyclic group include groups excluding one γ-petit rataton force hydrogen atom. Examples of the rataton-containing polycyclic group include a bicycloalkane, a tricycloalkane, and a tetracycloalkane having a rataton ring, in which one hydrogen atom is excluded. In particular, groups excluding one ratatotone-containing tricycloalkane hydrogen atom having the following structural formula are advantageous in terms of industrial availability, and the like.

 [Formula 4]

[0047] Further, as the structural unit (a4), those having a norbornane rataton are preferable among those which are a rataton-containing polycyclic group, and the like.

 [0048] In the structural unit (a4), another substituent may be bonded to the α-position (the carbon atom at the α-position) instead of a hydrogen atom. The substituent preferably includes an alkyl group, a fluorinated alkyl group, or a fluorine atom.

 These descriptions are the same as the description of R in the general formula (1) of the structural unit (al). (Of those capable of bonding at the X position, preferred is a hydrogen atom or an alkyl group, A hydrogen atom or a methyl group is preferred, and most preferably U is a hydrogen atom.

More specifically, examples of the structural unit (a4) include structural units represented by the following general formulas (a4-1) to (a4-5).

 (a4-2) (a4-3)

 (a4-4) a4-5

(In the formula, R is the same as described above. R ′ is each independently a hydrogen atom, an alkyl group, or an alkoxy group having 1 to 5 carbon atoms, and m is an integer of 0 or 1.)

The alkyl group of R ′ in the general formulas (a4-1) to (a4-5) is the same as the alkyl group of R in the structural unit (al). In the general formulas (a4-1) to (a4-5), R ′ is preferably a hydrogen atom in view of industrial availability.

As the structural unit (a4), the units represented by general formulas (a4-2) to (a4-3) are most preferable.

 As the structural unit (a4), one type may be used alone, or two or more types may be used in combination.

 [0054] Combination of structural units (al) to (a4)

 In the present invention, the structural units (al) to (a4) are preferably selected from, for example, four types of combinations as described below.

(I) Selection is made to include a combination of the structural unit (al) and the structural unit (a2). At this time, it is preferable that the structural unit (al) is a structural unit represented by the general formula (1), and R in the general formula (1) is a hydrogen atom. At the same time, a hydrogen atom is preferably bonded to the α-position (carbon atom to which a carboxyl group is bonded) of the structural unit (a2). The reason is that the dissolution contrast is improved.

(Ii) The selection is made to include a combination of the structural unit (al), the structural unit (a2), and the structural unit (a3).

 At this time, it is preferable that the structural unit (al) is a structural unit represented by the general formula (1), and that R in the general formula (1) is a hydrogen atom. At the same time, it is preferable that a hydrogen atom be bonded to the α-position of the structural unit (a2). The reason is that the dissolution contrast becomes better.

 (Iii) The selection is made to include a combination of the structural unit (al), the structural unit (a2), and the structural unit (a4).

 At this time, it is preferable that the structural unit (al) is a structural unit represented by the general formula (1), and R in the general formula (1) is a hydrogen atom. At the same time, a hydrogen atom is preferably bonded to the α-position of the structural unit (a2), and a hydrogen atom is preferably bonded to the a-position of the structural unit (a4).

 The reason is that the dissolution contrast is improved.

(Iv) The selection is made to include a combination of the structural unit (al), the structural unit (a2), the structural unit (a3), and the structural unit (a4).

 At this time, it is preferable that the structural unit (al) is a structural unit represented by the general formula (1), and R in the general formula (1) is a hydrogen atom. At the same time, a hydrogen atom is preferably bonded to the α-position of the structural unit (a2), and a hydrogen atom is preferably bonded to the a-position of the structural unit (a4).

 The reason is that the dissolution contrast is improved.

[0059] Ratio of structural unit (al) to structural unit (a4)

In the present invention, when the structural units (al) to (a4) are combined, they are classified into (i), (ii), (iii), and (iv) as described above. It is preferable to select a combination of the types. Therefore, the following is a description of the preferred constitutional units. Indicates a match.

 (i) Combination of structural unit (al) and structural unit (a2)

 At least two of the structural unit (al) and the structural unit (a2) are essential. Preferably, when the resin is composed of these two structural units, the ratio of each structural unit in the resin is in the following numerical range. Is preferably satisfied.

That is, the proportion of the structural unit (al) is preferably 20 to 80 mol%, more preferably 30 to 70 mole _^0/0, and most preferably 35 to 55 mole ^_0/0.

The proportion of the structural unit (a2) is preferably 20 to 80 mole _^0/0, more preferably 30 to 70 mol%, and most preferably 35 to 55 mole ^_0/0.

 By satisfying these ranges, the effect of suppressing swelling is improved.

[0060] (ii) Combination of structural unit (al), structural unit (a2), and structural unit (a3)

 It is a resin having the structural unit (al), the structural unit (a2), and the structural unit (a3), preferably, when the resin is composed of these structural units, the ratio of each structural unit in the resin Satisfies the following numerical range ヽ.

That is, the proportion of the structural unit (al) is preferably 20 to 80 mol%, more preferably from 3 0 to 70 mole _^0/0, and most preferably 35 to 55 mole ^_0/0.

The proportion of the structural unit (a2) is preferably 10 to 70 mole _^0/0, more preferably 10 to 50 mol%, more preferably from 20 to 40 mole ^_0/0.

The proportion of the structural unit (a3) is preferably 10 to 70 mole _^0/0, more preferably 10 to 40 mol%, and most preferably 15 to 35 mole ^_0/0.

 By satisfying these ranges, the effect of suppressing swelling is improved. In particular, by blending the structural unit (a2) and the structural unit (a3) in a well-balanced manner, an appropriate contrast is obtained and the resolution is improved. Further, etching resistance is improved. A better exposure latitude can be obtained.

[0061] (iii) Combination of structural unit (al), structural unit (a2), and structural unit (a4)

A resin having the structural units (al), (a2) and (a4), and preferably a resin comprising these structural units, the ratio of each structural unit in the resin satisfy the following numerical range. It is preferable to do so. That is, the proportion of the structural unit (al) is preferably 20 to 85 mol%, more preferably 3 0-70 mole _^0/0, and most preferably 35 to 50 mole ^_0/0.

The proportion of the structural unit (a2) is preferably 14 to 70 mole _^0/0, more preferably 15 to 50 mol%, and most preferably from 30 to 50 mole ^_0/0.

The proportion of the structural unit (a4) is preferably 1 to 70 mol _^0/0, more preferably 3 to 50 mol%, and most preferably 5 to 20 mol%.

 By satisfying these ranges, the effect of suppressing swelling is improved. In addition, the shape of the resist pattern is improved.

 Also, by blending (al), (a2) and (a4) in a well-balanced manner, an appropriate contrast is obtained and the resolution is improved. Further, etching resistance is improved. A better exposure latitude can be obtained.

(iv) Combination of structural unit (al), structural unit (a2), structural unit (a3), and structural unit (a4)

 It is a resin having all of the structural units (al) to (a4), and preferably a resin composed of these structural units, the ratio of each structural unit in the resin is in the following numerical range. It is preferable to satisfy the following.

That is, the proportion of the structural unit (al) is preferably 10 to 85 mol%, more preferably from 2 0 to 70 mole _^0/0, and most preferably 25 to 50 mole ^_0/0.

The proportion of the structural unit (a2) is preferably 10 to 80 mole _^0/0, more preferably 20 to 70 mol%, and most preferably from 30 to 50 mole ^_0/0.

The proportion of the structural unit (a3) is preferably 4 to 70 mol%, more preferably 7 to 50 mol%, and most preferably 10 to 30 mole ^_0/0.

The proportion of the structural unit (a4) is preferably 1 to 70 mol _^0/0, more preferably 3 to 50% by mole, and most preferably 5 to 20% by mole.

 By satisfying these ranges, the effect of suppressing swelling is further improved. Also, the resist pattern shape becomes good.

Also, by blending the structural units (al) to (a4) in a well-balanced manner, an appropriate contrast can be obtained and the resolution can be improved. Further, etching resistance is improved. further Good exposure latitude is obtained.

 The resin for a resist composition may have another copolymerizable structural unit other than the structural units selected from the structural units (al) to (a4). al) to structural unit (a4) It is preferable that the resin is a resin having a structural unit selected from the main components as a main component.

 Here, the main component is preferably such that the total of the constituent units for which these forces are also selected is 70 mol% or more, preferably 80 mol% or more, and particularly preferably 100%.

The resist composition for榭脂of the present invention, the structural units _(al) to the structural units of _(a4) (al) and the structural unit (a2) is required and that it has.

 [0064] With respect to the resin for a resist composition, particularly preferred are a resin having a structural unit (al) and a structural unit (a2) or a structural unit (al) and a structural unit (a2 ) And the structural unit (a3), or the structural unit (al), the structural unit (a2) and the structural unit (a4), the resin, or the structural unit (al) to the structural unit (a4) It is a resin having a high strength, more preferably a resin having a structural unit (al), a structural unit (a2) and a structural unit (a3).

 [0065] The weight average molecular weight (Mw; weight average molecular weight in terms of polystyrene by gel permeation chromatography) of the resin for a resist composition is preferably from 2000 to 30,000, more preferably from 2000 to 10,000, and most preferably. Is between 3000 and 8000. This range is preferable from the viewpoint of suppressing swelling and thereby suppressing microbridges. Also, high resolution point power is preferred. The lower the molecular weight, the better the properties tend to be.

 [0066] The resin for a resist composition can be obtained, for example, by subjecting a monomer for deriving each structural unit to radical polymerization by a conventional method.

 The resin for a resist composition of the present invention is preferably used for a negative resist composition.

 [Negative resist yarn and composition]

 The negative resist composition of the present invention contains (A) the resin for a resist composition of the present invention, (B) an acid generator component that generates an acid upon exposure, and (C) a crosslinking agent component.

(A) Resin for resist composition of the present invention

 The components (A) are as described above.

The component (A) can be used alone or in combination of two or more. The content of the component (A) may be adjusted according to the resist film thickness to be formed. (B) an acid generator component that generates an acid upon exposure

 The component (B) can be used without particular limitation from known acid generators used in conventional chemically amplified resist compositions.

 Examples of such acid generators include, for example, rhodium salt-based acid generators such as odonium salts and sulfo-dum salts, oxime sulfonate-based acid generators, bisalkyl or bisarylsulfol-diazomethanes, Various types are known, such as diazomethane acid generators such as poly (bissulfol) diazomethanes and nitrobenzylsulfonates, iminosulfonate acid generators, and disulfone acid generators.

Specific examples of the acid salt-based acid generator include trifluoromethanesulfonate or nonafluorobutanesulfonate of di-fluorodominium, trifluoromethanesulfonate or nonafluorobenoble of bis (4-tert-butylphenyl) iodenum. Tansulfonate, trifluoromethanesulfonate of triphenylsulfonium, heptafluorop mouth pansulfonate or nonafluorobutanesulfonate, tri (4-methylphenyl) norehone trifluoromethanesulfonate, heptafluorene Funoleolopropane snorephonate or its nonafluorobutane sulfonate, dimethyl (4-hydroxynaphthyl) snorefonium trifnoroleolomethanesnorephonate, its heptafanololepropane snorephonate or The nonafluorobutanesulfonate, the trifluorone methanesulfonate of monophenyl dimethylsulfonate, the heptafluoropropanesulfonate or the trifluorone of the nonafluorobutanesulfonate, diphenylmonomethylsulfonate Fluoromethanesulfonate, its heptafluoropropanesulfonate or its nonafluorobutanesulfonate, (4 methylphenyl) diphenylsulfo-dimethyl trifluoromethanesulfonate, its heptafluoropropanesulfonate or its nonafluorobutanesulfonate, ( 4-methoxyphenyl) diphenylsulfonium trifluoromethanesulfonate, its heptafluoropropanesulfonate or its nonafluorobutanesulfonate, tri (4-tert-butyl) phenyl Sulfo - © beam of triflate Ruo Lome drawers sulfonates, its like hepta full O b propane sulfonate or a nona Full O Rob Tan sulfonates and the like. [0071] Specific examples of the oxime sulfonate-based acid generator include: a (methylsulfo-roximino) -phenylacetonitrile, at- (methylsulfo- luximino) -p-methoxyphenylacetonitrile, α- (trifluoromethyl) Sulfo-Roxyimino) -Furea-ceto-tolyl, _α- (Trifluoromethylsulfo-Roxyimino) -p-Methoxyphenyl-acetonitrile, at- (Ethylsulfonyloxyminino) -p-Methoxyphenylacetonitrile, α- (Propylsulfo-roximinino) p-methylphenyl-acetonitrile, α (methylsulfo-roximinino) ρ-bromo-phenylacetonitrile and the like. Of these, α (methylsulfo-roxyimino) ρ-methoxyphenylacetitol is preferred.

 Among the diazomethane-based acid generators, specific examples of bisalkyl or bisarylsulfol-diazomethanes include bis (isopropylsulfol) diazomethane, bis (ρ toluenesulfol) diazomethane, and bis (1 , 1-dimethylethylsulfol) diazomethane, bis (cyclohexylsulfol) diazomethane, bis (2,4 dimethylphenylsulfol) diazomethane and the like.

Examples of the poly (bissulfonyl) diazomethanes include, for example, 1,3 bis (phenylsulfol-diazomethylsulfol) propane having the following structure (digestion compound Α, decomposition point 135 ° C) ), 1,4-bis (phenylsulfol-diazomethylsulfol) butane (compound B, decomposition point 147 ° C), 1,6-bis (phenylsulfol-l-diazomethylsulfol) hexane (Compound C, melting point 132 ° C, decomposition point 145 ° C), 1,10 bis (phenylsulfol-diazomethylsulfol) decane (disulfide compound D, decomposition point 147 ° C), 1,2 bis (Cyclohexylsulfol-l-diazomethylsulfol) ethane (I-conjugated product E, decomposition point 149 ° C), 1,3-bis (cyclohexylsulfol-l-dazomethylsulfol) propane Dagger F, decomposition point 153 ° C), 1,6 bis (cyclohexylsulfol-diazomethylsulfol) hexane ( Di-conjugated product G, melting point 109 ° C, decomposition point 122 ° C), 1,10 bis (cyclohexylsulfol-l-diazomethylsulfonyl) decane (di-conjugated product H, decomposition point 116 ° C) and the like. it can. [0073]

[0074] In the present invention, among others, from the viewpoint of the reactivity between the component (A) and the component (C), an aluminum salt having a fluorinated alkyl sulfonate ion as the component (B) is used as the component (B). It is preferable to use.

As the component (B), one type of acid generator may be used alone, or two or more types may be used in combination. May be used.

 The content of the component (B) is 0.5 to 30 parts by mass, preferably 1 to 10 parts by mass, based on 100 parts by mass of the component (A). With the above range, the pattern can be sufficiently formed. In addition, a uniform resist solution is obtained, and storage stability is improved.

 (C) Crosslinking agent component

 The component (C) is not particularly limited, and may be arbitrarily selected from crosslinker components used in chemically-amplified negative-type resist compositions known so far. it can.

 [0077] Specifically, for example, 2,3 dihydroxy-5 hydroxymethylnorbornane, 2 hydroxy 5,6-bis (hydroxymethyl) norbornane, cyclohexanedimethanol, 3,4,8 (or 9) -trihydroxy Aliphatic ring having a hydroxyl group or hydroxyalkyl group or both such as tricyclodecane, 2-methyl-2-adamantanol, 1,4 dioxane-1,2,3 diol, 1,3,5 trihydroxycyclohexane Examples thereof include hydrocarbons and oxygen-containing derivatives thereof.

 Further, an amino group-containing compound such as melamine, acetoguanamine, benzoguanamine, urea, ethylene urea, or glycol peryl is reacted with formaldehyde or formaldehyde and lower alcohol, and the hydrogen atom of the amino group is replaced with a hydroxymethyl group or a lower alkoxymethyl group. Substituted products are included.

 Of these, melamine-based products use melamine-based cross-linking agents, urea-based products use urea-based cross-linking agents, ethylene-urea-based products use ethylene-urea-based cross-linking agents, and With peryl crosslinking agents!

 Specific examples include hexamethoxymethyl melamine, bismethoxymethyl urea, bismethoxymethyl bismethoxyethylene urea, tetramethoxymethyldaricol peril, and tetrabutoxymethyl glycol peril.

 [0078] The component (C) is particularly preferably at least one selected from a melamine-based crosslinking agent, a urea-based crosslinking agent, an ethyleneurea-based crosslinking agent, and a glycolperyl-based crosslinking agent. Particularly preferred are glycol-peryl crosslinking agents.

[0079] The glycol peryl-based cross-linking agent includes glycol peryl substituted at the N-position with a hydroxyalkyl group or lower alkoxyalkyl group as a cross-linking group, or at the N-position. Glycol peryl substituted with a hydroxyalkyl group and a lower alkoxyalkyl group which are cross-linking groups are preferred!

 More specifically, examples of the glycoluril-based crosslinking agent include, for example, mono-, di-, tri- or tetrahydroxymethyldaricol-peryl, mono-, di-, tri- and / or tetramethoxymethyl-dalichol-peryl, mono-, di-, tri- And Z or tetraethoxymethyldaricol peril, mono, di, tri and Z or tetrapropoxymethyl iridyl glycol peryl, mono, di, tri and Z or tetrabutoxy methyl iridyl glycol peril and the like. “Mono, di, tri and / or tetra” means that one or more of the mono, di, tri and tetra is required. Is preferably a tri- ゃ tetra-isomer.

 Also preferred are mono, di, tri and / or tetramethoxymethyl iridyl glycol peryl, mono, di, tri and Z or tetrabutoxy methyl iridyl glycol peryl.

 From the viewpoints of contrast and resolution, mono, di, tri and / or tetramethoxymethylated glycol peryl is most preferred. This crosslinking agent can be obtained, for example, as a commercial product “Mx270” (product name, manufactured by Sanwa Chemical Co., Ltd.). These are mostly tri- and tetra-forms, and are mixtures of monomers, dimers and trimers.

 [0080] The compounding amount of the component (C) is 3 to 15 parts by mass, preferably 5 to 10 parts by mass, per 100 parts by mass of the component (A). When the amount is 3 parts by mass or more, the component (A) can be made alkali-insoluble. When the amount is 15 parts by mass or less, a decrease in resolution can be prevented. The fact that the smaller the amount of the crosslinking agent added, the higher the resolution tends to be, which is a characteristic of the negative resist composition of the present invention and is economically preferable. .

 [0081] (D) Nitrogen-containing organic compound

 The negative resist composition of the present invention further comprises a nitrogen-containing organic compound (D) (hereinafter referred to as component (D)) as an optional component in order to improve the resist pattern shape, the stability with time of storage, and the like. ) Can be blended.

 As the component (D), a wide variety of components have already been proposed, any known one may be used arbitrarily, and aliphatic amines, particularly secondary aliphatic amines ゃ tertiary aliphatic amines, are preferred. .

As the aliphatic amine, at least one of the hydrogen atoms of ammonia NH has at least 12 carbon atoms. Amines (alkylamines or alkylalcoholamines) substituted with an alkyl or hydroxyalkyl group below. Specific examples thereof include monoalkylamines such as n-hexylamine, n-butylamine, n-octylamine, n-norylamine, and n-decylamine; getylamine, di-n-propylamine, di-n-butylamine, di-n-octylamine. , Dicyclohexylamine and the like; trimethylamine, triethylamine, tri- _n -propylamine, tri-n-butylamine, tri-n-hexylamine, tri-n-pentylamine, tri-n-ptylamine, tri-n-octylamine, Trialkylamines such as tri-n-no-lamine, tri-n-de-lamine and tri-n-dodecylamine; diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, di- _n -o Kutanolamine, tree n —Alkyl alcoholamines such as octanolamine and the like.

 These may be used alone or in combination of two or more.

 Component (D) is generally used in an amount of 0.015.0 parts by mass with respect to 100 parts by mass of component (A). Of these, alkyl alcoholamines and trialkylamines are preferred, and alkyl alcoholamines are most preferred. Among the alkyl alcoholamines, an alkyl alcohol amine such as triethanolamine / triisopropanolamine is most preferable.

(E) component

 Further, for the purpose of preventing sensitivity deterioration due to blending with the component (D) and improving the resist pattern shape and the stability of the resist pattern, an organic carboxylic acid or an oxo acid of phosphorus or a derivative thereof as an optional component. (E) (hereinafter referred to as component (E)). The component (D) and the component (E) can be used in combination, or one of them can be used.

 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 oxo acids or derivatives thereof include phosphoric acid, phosphoric acid such as di-n-butyl phosphate and diphenyl phosphate, and derivatives such as esters thereof, phosphonic acid, dimethyl phosphonate, and phosphonic acid. -N-butyl ester, Hue- Derivatives such as phosphonic acids and their esters such as diphosphonic acid, diphenyl phosphonate and dibenzyl phosphonate, and derivatives such as phosphinic acids and esters thereof such as phosphinic acid and phenylphosphinic acid. Of these, phosphonic acid is particularly preferred.

 The component (E) is used in an amount of 0.01 to 5.0 parts by mass per 100 parts by mass of the component (A). The negative resist composition of the present invention can be produced by dissolving the constituent materials of the negative resist composition of the present invention in an organic solvent. The constituent materials of the negative resist composition of the present invention are (A) the resin for a resist composition of the present invention, (B) an acid generator component that generates an acid upon exposure, and (C) a crosslinking agent component. . The constituent material of the negative resist composition of the present invention contains at least one of the (D) nitrogen-containing organic compound and the (E) component in addition to the components (A) to (C). Yo,

 As the organic solvent, any one can be used as long as it can dissolve each component to be used and can form a uniform solution. The above can be appropriately selected and used.

 For example, ratatones such as γ-butyrolatatone, ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, and 2-heptanone; ethylene glycol, ethylene glycol monomonoacetate, diethylene glycol, and diethylene glycol Monoacetate, propylene glycol, propylene glycol monoacetate, dipropylene glycol or dipropylene glycol monoacetate, such as monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether or monophenyl ether and polyhydric alcohols and derivatives thereof, Cyclic ethers such as dioxane; methyl lactate, ethyl lactate (EL); methyl acetate; ethyl acetate; butyl acetate; methyl pyruvate; Acid Echiru, methyl methoxypropionate, and the like esters such as ethoxy propyl propionic acid Echiru.

These organic solvents may be used alone or as a mixed solvent of two or more. Further, a mixed solvent obtained by mixing propylene glycol monomethyl ether acetate (PGMEA) and a polar solvent is preferable. The mixing ratio (mass ratio) may be appropriately determined in consideration of the compatibility between PGMEA and the polar solvent, but is preferably 1: 9 to 9: 1, more preferably 2: 1 to 9: 1. : 8 to 8: preferably in the range of 2! / ,.

 More specifically, when EL is blended as a polar solvent, the mass ratio of PGMEA: EL is preferably 2: 8 to 8: 2, more preferably 3: 7 to 7: 3! / ,.

 Further, as the organic solvent, a mixed solvent of at least one selected from PGMEA and EL and γ-petit mouth rataton is also preferable. In this case, the mixing ratio of the former and the latter is preferably 70: 30-95: 5.

 As the organic solvent, propylene glycol monomethyl ether (PGME) is also preferable.

 Although the amount of the organic solvent used is not particularly limited, it is a concentration that can be applied to a substrate or the like and is appropriately set according to a coating film thickness. Generally, the solid content concentration of the resist composition is 2 to 20 mass %, Preferably in the range of 5 to 15% by mass.

[0084] The negative resist composition of the present invention may contain other optional components in addition to the above-mentioned components, and if necessary, improve the performance of a miscible additive such as a resist film. A surfactant, a dissolution inhibitor, a plasticizer, a stabilizer, a colorant, an antihalation agent, a dye, and the like for improving the application of the resin and the coatability can be appropriately added and contained.

 [0085] The negative resist composition of the present invention is not particularly limited, but is suitable for processes using an ArF excimer laser as an exposure light source.

 The process requires high resolution, and in the negative resist composition of the present invention, various properties such as resolution are improved by suppressing swelling. This is because such strict requirements can be met.

 Another reason is that a structure having high transparency to an ArF excimer laser can be obtained.

 [0086] [Method of forming resist pattern]

 The method of forming a resist pattern comprises applying the negative resist composition of the present invention onto a substrate, pre-betaing (PAB), selectively exposing, subjecting to PEB (heating after exposure), and developing an alkaline image to form a resist pattern. To form

The method of forming a resist pattern according to the present invention can be performed, for example, as follows. That is, first, the negative resist composition is applied on a substrate such as silicon wafer with a spinner or the like. Next, the negative resist composition is applied with a prebeta at a temperature of 80 to 150 ° C. for 40 to 120 hectares, preferably 60 to 90 hectares. Next, the pre-stressed resist film is selectively exposed to ArF excimer laser light through a desired mask pattern using, for example, an ArF exposure device. Then, PEB (post-exposure bake) is applied to the selectively exposed resist film at a temperature of 80 to 150 ° C. for 40 to 120 seconds, preferably 60 to 90 seconds. Next, in an alkali developer of the resist film subjected to the PEB, e.g. 0.1 to 10 weight _^0/0 tetramethylammonium - development processing using Umuhidorokishido solution. In this way, a resist pattern faithful to the mask pattern can be obtained. Note that an organic or inorganic antireflection film can be provided between the substrate and the coating layer of the resist composition.

[0087] The wavelength used for the exposure is not particularly limited. ArF excimer laser, KrF excimer laser, F excimer laser, EUV (extreme ultraviolet), VUV (vacuum ultraviolet), EB (electron beam),

2

 It can be performed using radiation such as X-rays and soft X-rays. In particular, the resist composition according to the present invention is effective for ArF excimer laser as described above.

In the present invention, swelling of the resist pattern can be prevented. Thereby, the micro bridge can be suppressed. Further, the resolution is improved. In addition, the depth of focus characteristic is improved. Also, LER (Lie Edge Roughness) can be suppressed. Note that LER is uneven unevenness on the line side wall.

 In addition, the effect of improving the stability over time can be obtained.

 Example

 [Monomer used in Synthesis Example]

 In the synthesis examples, the following monomers were used.

(i) NBHFAA (norbornene hexafluoro alcohol acrylate) represented by the following chemical formula, molecular weight 340 [0090] [Formula 7]

[0091] (ii) HEMA (hydroxyethyl methacrylate) represented by the following chemical formula, molecular weight 130

(Iii) AdOHA (adamantanol acrylate) represented by the following chemical formula, molecular weight 222

[0094] [Formula 9]

[0095] (iv) RHMA—E [(a-hydroxymethyl) ethytaltalate] represented by the following chemical formula:

, Molecular weight 130

[0096] [Formula 10]

(V) RHMA—M [(a-hydroxymethyl) methyl atalylate] represented by the following chemical formula, molecular weight 116

[0098] [Formula 11]

 (vi) GBLA (γ-petit mouth ratatone acrylate) represented by the following chemical formula: molecular weight 116

[0099] [Formula 12]

(vii) NBLA (norbornane ratatone acrylate) represented by the following chemical formula: molecular weight 222

[0100] [Formula 13]

H _? C

[0101] [Synthesis example]

 In this synthesis example, NMR (Nuclear Magnetic Resonance) was measured using JNM-AL400 (product name, resolution 400 MHz) manufactured by JEOL Ltd.

 • Synthesis example 1

 9.19 g of NBHFAA, 3.51 g of HEMA, 6.0 g of AdOHA, and 0.6 g of dimethyl azobisisoacetate as a polymerization initiator were dissolved in 200 ml of THF (tetrahydrofuran). Next, the solution was subjected to nitrogen publishing for about 10 minutes, stirred for 4 hours while heating using an oil bath at 70 ° C., and then cooled to room temperature. Next, after the reaction solution was concentrated by an evaporator, the concentrate was dissolved in 120 ml of THF, and poured into 1000 ml of heptane to precipitate a resin, followed by filtration. The obtained resin was dried in a drier at 40 ° C. for 24 hours to obtain 15.6 g of a white solid (yield: 83.4%).

The obtained resin is represented by the following chemical formula (4). Its mass average molecular weight (Mw) was 14,400, and the dispersion (MwZMn; Mw was the mass average molecular weight, Mn was the number average molecular weight) was 1.86. Was confirmed by carbon NMR, the composition ratio (mol _^0/0) was lZmZn = 33Z33Z33. This is referred to as resin 1. [0102] [Formula 14]

[0103] Synthesis example 2

 13.58 g of NBHFAA, 3.51 g of HEMA, 6.0 g of AdOHA, and 0.7 g of dimethyl azobisisoacetate as a polymerization initiator were dissolved in 200 ml of THF (tetrahydrofuran). This solution was subjected to nitrogen publishing for about 10 minutes, stirred for 4 hours while heating using an oil bath at 70 ° C, and then cooled to room temperature. Next, after the reaction solution was concentrated by an evaporator, the concentrated solution was dissolved in 120 ml of THF, and poured into 1000 ml of heptane to precipitate a resin, followed by filtration. The obtained resin was dried in a drier at 40 ° C. for 24 hours to obtain 21.1 g of a white solid (yield: 91.4%).

The chemical formula of the obtained resin is the same as the above chemical formula (4). Its mass average molecular weight (M w) was 18,200 and the degree of dispersion (MwZMn) was 2.20. Was confirmed by carbon NMR, the composition ratio (mol _^0/0) was lZmZn = 42. 5/28. 75/28. 75. This is referred to as resin 2.

[0104] Synthesis example 3

17.58 g of NBHFAA, 3.51 g of HEMA, 6.50 g of AdOHA, and 0.87 g of dimethyl azobisisoacetate as a polymerization initiator were dissolved in 200 ml of THF (tetrahydrofuran). Next, this solution was subjected to nitrogen publishing for about 10 minutes, stirred for 4 hours while heating using an oil bath at 70 ° C, and then cooled to room temperature. Next, after concentrating the reaction solution with an evaporator, the concentrated solution was dissolved in 120 ml of THF, and poured into 1000 ml of heptane to precipitate a resin, followed by filtration. The obtained resin is dried in a dryer at 40 ° C for 24 hours to obtain a white solid. 23.9 g obtained (yield 88.2%) o

The chemical formula of the obtained resin is the same as the above chemical formula (4). Its mass average molecular weight (M w) was 17,400 and the degree of dispersion (MwZMn) was 2.40. Was confirmed by carbon NMR, the composition ratio (mol _^0/0) was lZmZn = 49Z25. 5/25. 5. This is referred to as resin 3.

[0105] Synthesis example 4

 13.58 g of NBHFAA, 1.76 g of HEMA, 6.0 g of AdOHA, and 0.6 g of dimethyl azobisisoacetate as a polymerization initiator were dissolved in 200 ml of THF (tetrahydrofuran). Next, the solution was subjected to nitrogen publishing for about 10 minutes, stirred for 4 hours while heating using an oil bath at 70 ° C., and then cooled to room temperature. Next, the reaction solution was concentrated by an evaporator, and then the concentrated solution was dissolved in THF (120 ml) and poured into heptane (1000 ml) to precipitate a resin, followed by filtration. The obtained resin was dried in a drier at 40 ° C. for 24 hours to obtain 18.8 g of a white solid (yield: 88.0%).

The chemical formula of the obtained resin is the same as the above chemical formula (4). Its mass average molecular weight (M w) was 5,900 and dispersity (MwZMn) was 1.98. Rollers and was confirmed by carbon NMR, the composition ratio (mol _^0/0) was lZmZn = 50Zl7Z33. This is referred to as resin 4.

[0106] Synthesis example 5

 13.58 g of NBHFAA, 6.0 g of AdOHA, and 0.5 g of dimethyl azobisisoacetate as a polymerization initiator were dissolved in 200 ml of THF (tetrahydrofuran). Then, the solution was subjected to nitrogen publishing for about 10 minutes, stirred for 4 hours while heating using an oil bath at 70 ° C, and then cooled to room temperature. Next, after the reaction solution was concentrated by an evaporator, the concentrated solution was dissolved in 120 ml of THF, and poured into 1000 ml of heptane to precipitate a resin, followed by filtration. The obtained resin was dried in a dryer at 40 ° C. for 24 hours to obtain 14.lg of a white solid (yield: 72.0%).

The chemical formula of the obtained resin is chemical formula (5). Its mass average molecular weight (Mw) was 4000 and the degree of dispersion (MwZMn) was 1.59. Was confirmed by carbon NMR, the composition ratio (mol _^0/0) was lZn = 60Z40. This is referred to as resin 5 (decomposition point: 293 ° C, Tg: 105 ° C

) o [0107] [Formula 15]

[0108] Synthesis example 6

 13.3 g of NBHFAA, 3.51 g of HEMA, 6.0 g of AdOHA, and 0.7 g of dimethyl azobisisoacetate as a polymerization initiator were dissolved in 200 ml of THF (tetrahydrofuran). Then, the solution was subjected to nitrogen publishing for about 10 minutes, stirred for 4 hours while heating using a 70 ° C. oil bath, and then cooled to room temperature. Next, the reaction solution was concentrated by an evaporator, and then the concentrated solution was dissolved in THF (120 ml) and poured into heptane (1000 ml) to precipitate a resin, followed by filtration.

 The obtained resin was dried in a drier at 40 ° C. for 24 hours to obtain 19.8 g of a white solid (yield 86.8%).

The chemical formula of the obtained resin is the same as the above chemical formula (4). Its mass average molecular weight (M w) was 5,500 and the degree of dispersion (MwZMn) was 1.90. Rollers and was confirmed by carbon NMR, the composition ratio (mol _^0/0) was lZmZn = 39. 9/29. 4/30. 7 . This is called resin 6. The results of proton nuclear magnetic resonance spectrum ^ H-NMR) and infrared absorption spectrum (IR) were as follows.

IR (cm ^_1 ): 3350 (-OH), 295K-CH CH-), 1730 (C = O), 1456 (-CH-), 1072 (

 2 3 2

^{C-OH) J H - NMR} (DMSO - d, internal standard:. Tetramethylsilane) ppm: 1~2 3 (m,

 6

 36H), 3.5 (s, 2H), 3.9 (s, 2H), 4.4-4.8 (m, 3H), 7.7 (d, 1H) Decomposition point: 225 ° CTg: 102 ° C

[0109] Synthesis example 7 7.87 g of NBHFAA, 3.51 g of HEMA, 6.60 g of AdOHA, and 0.58 g of dimethyl azobisisoacetate as a polymerization initiator were dissolved in 200 ml of THF (tetrahydrofuran). Next, the solution was subjected to nitrogen publishing for about 10 minutes, stirred for 4 hours while heating using an oil bath at 70 ° C., and then cooled to room temperature. Next, the reaction solution was concentrated by an evaporator, and then the concentrated solution was dissolved in THF (120 ml) and poured into heptane (1000 ml) to precipitate a resin, followed by filtration. The obtained resin was dried in a dryer at 40 ° C. for 24 hours to obtain 14.9 g of a white solid (yield: 85.7%).

The chemical formula of the obtained resin is the same as the above chemical formula (4). Its mass average molecular weight (M w) was 6,500, and its dispersity (MwZMn) was 2.23. Rollers and was confirmed by carbon NMR, the composition ratio (mol _^0/0) was lZmZn = 30Z35Z35. This is referred to as resin 7. 'Synthesis example 8

 13.3 g of NBHFAA, 3.51 g of RHMA-E, 6.0 g of AdOHA, and 0.7 g of dimethyl azobisisoacetate as a polymerization initiator were dissolved in 200 ml of THF (tetrahydrofuran). Next, this solution was subjected to nitrogen publishing for about 10 minutes, stirred for 4 hours while heating using an oil bath at 70 ° C, and then cooled to room temperature. Next, after concentrating the reaction solution with an evaporator, the concentrated solution was dissolved in 120 ml of THF, and poured into 1000 ml of heptane to precipitate a resin, followed by filtration. The obtained resin was dried in a drier at 40 ° C. for 24 hours to obtain 21.Og of a white solid (yield 92.0%).

The chemical formula of the obtained resin is the following chemical formula (6). Its mass average molecular weight (Mw) was 5570 and the degree of dispersion (MwZMn) was 2.02. Was confirmed by carbon NMR, set composition ratio (mol _^0/0) was lZmZn = 35. 8/26. 3/37. 9 . This is referred to as resin 8. The results of proton nuclear magnetic resonance spectrum ^ H-NMR) and infrared absorption spectrum (IR) were as follows.

 IR (cm—: 3388 (—OH), 2948 (-CH CH-), 1730 (C = O), 1452 (-CH-), 1052 (

 2 3 2

(C-OH) 'H-NMRCDMSO, internal standard: tetramethylsilane) ppm: l ~ 2.3 (m, 36H), 3.5 (Broad, 2H), 4.0 (s, 2H), 4. 4-4.8 (d, 3H), 7.7 (d, 1H) Decomposition point: 238 ° CTg: 94 ° C

[0111] [Formula 16]

[0112] 'Synthesis example 9

 9.50 g of NBHFAA, 21 g of HEMA, and 2.07 g of AdOHA, and 0.35 g of dimethyl azobisisoacetate as a polymerization initiator were dissolved in 100 ml of THF (tetrahydrofuran). Next, this solution was subjected to nitrogen publishing for about 10 minutes, stirred for 4 hours while heating using an oil bath at 70 ° C, and then cooled to room temperature. Next, after concentrating the reaction solution with an evaporator, the concentrate was dissolved in 60 ml of THF, and poured into 1000 ml of heptane to precipitate a resin, followed by filtration. The obtained resin was dried in a drier at 40 ° C. for 24 hours to obtain 11.5 g of a white solid (yield: 90.0%).

The chemical formula of the obtained resin is the same as the above chemical formula (4). Its mass average molecular weight (M w) was 6,600, and dispersity (MwZMn) was 2.15. Rollers and was confirmed by carbon NMR, the composition ratio (mol _^0/0) was lZmZn = 60Z20Z20. This is referred to as resin 9.

[0113] 'Synthesis example 10

NBHFAA 12.66 g, HEM AO. 6 g, and AdOHAl. 03 g, and a polymerization initiator 0.35 g of dimethyl azobisisoacetate was dissolved in 100 ml of THF (tetrahydrofuran). Next, this solution was subjected to nitrogen publishing for about 10 minutes, stirred for 4 hours while heating using an oil bath at 70 ° C, and then cooled to room temperature. Next, after concentrating the reaction solution with an evaporator, the concentrated solution was dissolved in 60 ml of THF, and poured into 2000 ml of heptane to precipitate a resin, which was filtered. The obtained resin was dried in a drier at 40 ° C. for 24 hours to obtain 10.63 g of a white solid (yield: 74.3%).

The chemical formula of the obtained resin is the same as the above chemical formula (4). Its mass average molecular weight (M w) was 6,100 and the degree of dispersion (MwZMn) was 1.52. Rollers and was confirmed by carbon NMR, the composition ratio (mol _^0/0) was lZmZn = 80ZlOZlO. This is referred to as resin 10. '' Synthesis example 11

 30 g of NBHFAA and 0.70 g of dimethyl azobisisoacetate as a polymerization initiator were dissolved in 200 ml of THF (tetrahydrofuran). Next, the solution was subjected to nitrogen publishing for about 10 minutes, stirred for 4 hours while heating using an oil bath at 70 ° C, and then cooled to room temperature. Next, after concentrating the reaction solution with an evaporator, the concentrated solution was dissolved in 120 ml of dioxane, and poured into 4800 ml of pure water to precipitate a resin, which was filtered. The obtained resin was dried in a dryer at 40 ° C. for 24 hours to obtain 10.64 g of a white solid (yield 53.2%).

The chemical formula of the obtained resin is as shown in the following chemical formula (7). Its mass average molecular weight (Mw) was 3,800, and dispersity (MwZMn) was 1.37. This is referred to as resin 11.

[0115] [Formula 17]

[0116] 'Synthesis example 12

 2.73 g of methacrylic acid, 16.5 g of RHMA-E1 and azobisisobutymouth-triol 1.Og as a polymerization initiator were dissolved in 300 ml of THF (tetrahydrofuran). Next, the solution was subjected to nitrogen bubbling for about 10 minutes, stirred for 4 hours while heating using an oil bath at 70 ° C., and then cooled to room temperature. Next, after the reaction solution was concentrated by an evaporator, the concentrated solution was dissolved in 150 ml of THF, and poured into a mixed solvent of 850 ml of heptane and 150 ml of isopropyl alcohol to precipitate a resin, followed by filtration. The obtained resin was dried in a dryer at 40 ° C. for 24 hours to obtain 11.75 g of a white solid (yield: 63.2%).

 The chemical formula of the obtained resin is as shown in the following chemical formula (8). Its mass average molecular weight (Mw) was 9,700 and the degree of dispersion (MwZMn) was 1.76. This is referred to as resin 12.

Was confirmed by carbon NMR, the composition ratio (mol _^0/0) was mZn = 20Z80

[0117] [Formula 18]

[0118] The composition (mol%), mass average molecular weight, and dispersity of the resins obtained in Synthesis Examples 1 to 12 were summarized.

¾kl.

[0119] [Table 1]

[0120] [Production of resist composition]

 The materials shown in Table 2 were mixed to produce negative resist compositions of Examples and Comparative Examples.

 The amount of the solvent used was adjusted so that the resist solid content concentration was about 8% by mass.

[0121] [Table 2] (D) Nitrogen containing

 (A) Resin (B) Acid generator (C) Crosslinker Organic solvent

 Organic compounds

 榭 脂 1 TPS-PFBS Binderl Triisov 'U! \' Luamine Example 1 PGWE

 (100W parts) (2 parts) parts) .4 parts)

 Resin 2 TPS-PFBS Binder! Triisophor 'Ql \' Luamine Example 2 PGME

 (100 parts by mass) (2 parts by mass) (10 parts by mass) (0.4SS part)

 Resin 3 TPS-PFBS Binderl Triisophthalamine Example 3 PGME

 (100 parts by weight) (2 parts by weight) (10 K parts by weight) (0.4 g part by weight)

 Resin 9 TPS-TF Binderl Triisoa DA 'Nolamine Example 4 PGME

 (100 parts by mass) (2H part) (5S part) (0.4 storage part)

 Resin 9 TPS-TF Binderl Triisov 'ΡΛ'-noramine Example 5 PGME

 (100 lights) (2 parts by mass) (10S amount) (0.4 quality part)

 Resin 5 TPS-TF Binderl Tosof 'D / \' noramine Example 6 PG E

 (100M part) (2K part) (5K part) (0.4g part)

 Resin 4 TPS-TF Binder!

 Example 7 / one run

 PGME

 Parts) (2g parts) 00 parts by mass> (0,4 quality S part) Resin 4 TPS-TF Binderl Triisov 'fl / V J-A7V / Example 8 PGME

 (100S part) (2 parts by mass) (5g part) (0.4K 轚 part)

 Resin 6 TPS-TF Binderl Triisoa α-noramine Example 9 PGME

 (100 parts by weight) (2 parts by weight) (10 parts by weight) (0.4 quality S part)

 Resin S TPS-TF Binderl Triiso; αha '/-lamine Example 10 PGME

 (100 trade department) (2K quantity department) (5S quantity department) (0.4 quality section)

 Resin 8 TPS-TF Binderl Trinov 'Nol 7min Example 11 PGME

 (100 parts by mass) (2 bins) (5 parts by mass) (0.4S parts)

 Resin 1 1 TPS-TF Binderl Triisof 'P / V Knol 7min Ratio ■ 1 PGME

 (ιοοΚ parts) (2 parts by weight) (10S parts) (0.4 parts by weight)

 Resin 1 2 TPS-PFBS Binder2 4—F

 Comparative Example 2 PGME

 (100 parts by mass) (1K parts) (10 parts by mass) (0.4 parts by mass)

 TPS-PFBS → triphenylsulfonidum nonafluorobutanesulfonate

 TPS-TF → triphenylsulfonium trifluoromethanesulfonate

 Binderl → M x270 (product name, manufactured by Sanwa Chemical Co., Ltd.)

 Tetramethoxymethylated glycoperyl

 Binder2 → E6301 (Product name, manufactured by Sanwa Chemical Co., Ltd.)

 Tetrabutoxymethylated glycoperyl

[Evaluation]

 The negative resist compositions of Examples and Comparative Examples were evaluated as follows.

Organic anti-reflective coating composition “AR-19” (trade name, manufactured by Shipley) is applied on an 8-inch silicon wafer using a spinner, baked on a hot plate at 215 ° C for 60 seconds, and dried. As a result, an organic antireflection film having a film thickness shown in Table 3 was formed. Then, the negative resist composition manufactured as described above is applied on an antireflection film using a spinner, pre-betaed (PAB) on a hot plate under the conditions shown in Table 3, and dried to obtain the composition shown in Table 3. A resist layer having a thickness was formed.

 Next, an ArF excimer laser (193 nm) was selectively irradiated through a mask pattern (binary) using an ArF exposure apparatus NSR-S302 (manufactured by Nikon Corporation; NA (numerical aperture) = 0.60, 2Z3 orb). .

 Then, PEB treatment was performed under the conditions shown in Table 3, followed by paddle development at 23 ° C with a 2.38% by weight aqueous solution of tetramethylammonium hydroxide for 60 seconds, followed by washing with water for 20 seconds and drying to form a resist pattern. Formed.

[0123] At this time, in the example, in a 140 nm line-and-space pattern (denoted as L & S or LS), the exposure amount (sensitivity) at which the width of the line and space was formed at 1: 1 was obtained. For the comparative example, the exposure amount (sensitivity) at which the line and space width was 1: 1 in a 160 nm line and space pattern (L & S) was determined.

 Then, by changing the size of the L & S pattern, the limit resolution (resolution evaluation) that can be resolved with this exposure amount was determined.

 Further, the cross-sectional shape of the pattern was observed with a scanning electron microscope to evaluate swelling.

 Table 4 shows the results.

[0124] [Table 3]

Register

 Substrate Anti-reflective coating PAB PEB

 Film thickness

 8 inch AR ~ 1 9

Example 1 200 nm 90 ° C / 60 seconds 100/60 seconds Silicon A 8 8 r> m

 8 inch AR—1 9

Example 2 200 nm 90ΐ: / 60 sec. At 100/60 sec.

 S-inch AR-1 9

Example 3 200 nm 90 ° C / 60 sec. 100 ° C / 60 sec.

 8inch AR-1 9

Jeongjeon 4 200nm 8CTC / 60 seconds 100. C no 60¾ *

 Silicon wafer 8 2 nm

 8 inches

Actual example 5 200nm 8CTC / 60sec 100. C / 60 seconds Silicone 18

 8 inch

Example 6 200 nm 80 ° C / 60 sec. 100 ° C No. 60 sec.

 8 inch> AR-1 9

Example 7 200 nm 80 ° C / 60 seconds 100 ° C / 60 seconds Silicon wafer 82 nm

 8-inch AR—Co * 1 _ 9

 II Example 8 200nm 80 ^ C / 60sec 100 ° C / 60sec Silicon layer 82nm

 8inch AR-1 9

Example 9 200 nm 80. C / 60 sec 100 ° C / 60 sec Silicon wafer 8 2 nm

 8-inch AR—1 9

Example 10 200 nm 80 = 0/60 sec. 1001 C / 60 sec.

 8 inch AR-1 9

Example 1 1 200nm 80¾ / 60sec 10CTC / 60sec Silicon wafer & 2nm

 8 inch AR-1 9

Comparative Example 1/60 sec at 200nm 80

 Silicone 18 2 nm

 8 inch AR-1 9

Comparative Example 2 300 nm 1 10 t / 60 sec nO ° C / 60 sec Silicon wafer 8 2 nm

AR—19 → Product name, Shipley's organic anti-reflective coating

Resolution Pattern shape * ² Sensitivity * ¹

 Example 1 130 nm L S © ^ mJ / cm ^

Example 2 120 nm LS ◎ 41 m J / cm ²

Example 3 130 nm SQ 42 mJ / cm ²

Example 4 120 nm LS ◎ 29 mJ / cm ²

 Example 5 120 nm L S ◎ 32 mJ / cm

Example 6 130 nm LS 〇 29 mj / cm ²

Example 7 150 nm LS 〇 31 mJ / cm ²

Example 8 1 2 O nm LS © 30 mJ / cm ²

Example 9 12 O nm LSO 29 mJ / cm ²

Example 10 13 nm nm LS © 27 mJ / cm ²

Example 1 1 1 2 0 nm LS 〇 31 mJ / cm ²

 Comparative Example 1 No resolution--

Comparative Example 2 l 6 O nm SX 20 mJ / cm ²

 1 Sensitivity is the sensitivity at which an L & S pattern of 1400 nm 1: 1 is obtained

 (Comparative example is "I 60 nm 1: 1 L & S pattern").

 ◎ —Rectangular resist pattern without swelling

 There is a slight expansion in the 部分 → τορ part,

 The resist pattern had a good rectangularity without any practical problem.

 χ—The resist pattern had severe swelling.

From the results shown in Table 4, it was confirmed that in Examples according to the present invention, swelling was suppressed and a fine resist pattern could be formed.

[0127] 'Synthesis example 13

 13.3 g of NBHFAA, 13 g of RHMA-M, 13 Og of AdOHA, and 0.7 g of dimethyl azobisisoacetate as a polymerization initiator were dissolved in 200 ml of THF (tetrahydrofuran). Next, this solution was subjected to nitrogen bubbling for about 10 minutes, stirred for 4 hours while heating using an oil bath at 70 ° C, and then cooled to room temperature. Next, after concentrating the reaction solution with an evaporator, the concentrated solution was dissolved in 120 ml of THF, and poured into 1000 ml of heptane to precipitate a resin, followed by filtration. The obtained resin was dried in a drier at 40 ° C. for 24 hours to obtain 14.9 g of a white solid (yield: 66.5%).

The chemical formula of the obtained resin is the following chemical formula (9). Its mass average molecular weight (Mw) was 6,300 and the degree of dispersion (MwZMn) was 1.83. Was confirmed by carbon NMR, set composition ratio (mol _^0/0) was lZmZn = 42Z29Z29. This is referred to as resin 13. [0128] [Formula 19]

[0129] 'Synthesis example 14

 13.3 g of NBHFAA, 3.51 g of HEMA, 6.0 g of AdOHA, and 0.7 g of dimethyl azobisisoacetate as a polymerization initiator were dissolved in 200 ml of THF (tetrahydrofuran). Next, the solution was subjected to nitrogen publishing for about 10 minutes, stirred for 4 hours while heating using an oil bath at 70 ° C., and then cooled to room temperature. Next, after concentrating the reaction solution with an evaporator, the concentrate was dissolved in 150 ml of THF, and poured into 1000 ml of heptane to precipitate a resin, followed by filtration. Next, the precipitated resin was taken out, dissolved in 150 ml of THF, and poured into 2,000 ml of heptane to precipitate the resin, followed by filtration. The obtained resin was dried in a drier at 40 ° C. for 24 hours to obtain 19.8 g of a white solid (yield: 86.8%).

 The obtained resin is represented by the chemical formula (4). Its mass average molecular weight (Mw) was 7,500, and its dispersion (MwZMn) was 2.15.

Was confirmed by carbon NMR, the composition ratio (mol _^0/0) was lZmZn = 42Z42Z29. This is referred to as resin 14.

[0130] 'Synthesis example 15

13.3 g of NBHFAA, 2.54 g of HEMA, 4.34 g of AdOHA and 0.7 g of dimethyl azobisisoacetate as a polymerization initiator were dissolved in 200 ml of THF (tetrahydrofuran). next This solution was subjected to nitrogen publishing for about 10 minutes, and the mixture was stirred for 4 hours while heating using a 70 ° C oil bath, and then cooled to room temperature. Next, the reaction solution was concentrated by an evaporator, and the concentrated solution was dissolved in 150 ml of THF, and poured into 1000 ml of heptane to precipitate a resin, followed by filtration. Next, the precipitated resin was taken out, dissolved in 150 ml of THF, and poured into 2000 ml of heptane to precipitate the resin, followed by filtration. The obtained resin was dried in a drier at 40 ° C. for 24 hours to obtain 14.9 g of a white solid (yield: 73.8%).

 The obtained resin is represented by the chemical formula (4). Its mass average molecular weight (Mw) was 6,500 and the degree of dispersion (MwZMn) was 1.92.

Was confirmed by carbon NMR, the composition ratio (mol _^0/0) was lZmZn = 50Z25Z25. This is referred to as resin 15.

[0131] · Synthesis example 16

 9.1 g of NBHFAA, 6.0 g of AdOHA, and 0.5 g of dimethyl azobisisoacetate as a polymerization initiator were dissolved in 200 ml of THF (tetrahydrofuran). Next, the solution was subjected to nitrogen bubbling for about 10 minutes, stirred for 4 hours while heating using an oil bath at 70 ° C., and then cooled to room temperature. Next, after the reaction solution was concentrated by an evaporator, the concentrated solution was dissolved in THF, and poured into 2,000 ml of heptane to precipitate a resin, followed by filtration. The obtained resin was dried in a drier at 40 ° C. for 24 hours to obtain 11.4 g of a white solid (yield: 75.0%).

The chemical formula of the obtained resin is the above-mentioned chemical formula (5). Its mass average molecular weight (Mw) was 3100 and the degree of dispersion (MwZMn) was 1.68. Was confirmed by carbon NMR, set composition ratio (mol _^0/0) was lZn = 60Z40. This is referred to as resin 16.

[0132] 'Synthesis example 17

12.25 g of NBHFAA, 34 g of HEMA, 6.0 g of AdOHA and 1.40 g of GBLA and 0.7 g of dimethyl azobisisoacetate as a polymerization initiator were dissolved in 200 ml of THF (tetrahydrofuran). Next, the solution was subjected to nitrogen publishing for about 10 minutes, stirred for 4 hours while heating using an oil bath at 70 ° C, and then cooled to room temperature. Next, after the reaction solution was concentrated by an evaporator, the concentrated solution was dissolved in 200 ml of THF, and poured into 2,000 ml of heptane to precipitate a resin, followed by filtration. The obtained resin is dried in a dryer at 40 ° C for 24 hours. As a result, 10.9 g of a white solid was obtained (yield: 49.6%).

 The obtained resin is represented by the following chemical formula (10). Its mass average molecule

 The dispersity (MwZMn) was 2.23.

 Confirmed by carbon NMR, the composition ratio (mol%) was lZmZ

 It was 30Z10. This is referred to as resin 17.

[0133] [Formula 20]

[0134] 'Synthesis example 18

12.25 g of NBHFAA, 34 g of HEMA, 6.0 g of AdOHA, and 2.0 g of NBLA, and 0.7 g of dimethyl azobisisoacetate as a polymerization initiator were dissolved in 200 ml of THF (tetrahydrofuran). Next, the solution was subjected to nitrogen publishing for about 10 minutes, stirred for 4 hours while heating using an oil bath at 70 ° C, and then cooled to room temperature. Next, after concentrating the reaction solution with an evaporator, the concentrated solution is dissolved in 200 ml of THF and poured into 2000 ml of heptane. The resin was precipitated by filtration and filtered. The obtained resin was dried in a drier at 40 ° C. for 24 hours to obtain 13.9 g of a white solid (yield: 61.5%).

 The obtained resin is represented by the following chemical formula (11). Its mass average molecular weight (Mw) was 5,600 and its dispersion (MwZMn) was 2.24.

Was confirmed by carbon NMR, it was a composition ratio (mol _{^{0/0) «l / m}} / n / o = 40/20 / 30Z10. This is called resin 18.

[0135] [Formula 21]

[0136] 'Synthesis example 19

 9.19 g of NBHFAA, 6.33 g of AdOHA, and 1.33 g of NBLA, and 0.7 g of dimethyl azobisisoacetate as a polymerization initiator were dissolved in 200 ml of THF (tetrahydrofuran). Next, this solution was subjected to nitrogen publishing for about 10 minutes, stirred for 4 hours while heating using an oil bath at 70 ° C, and then cooled to room temperature. Next, after concentrating the reaction solution with an evaporator, the concentrate was dissolved in 200 ml of THF, and poured into 2000 ml of heptane to precipitate a resin, followed by filtration. The obtained resin was dried in a drier at 40 ° C. for 24 hours to obtain 13.3 g of a white solid (yield: 80.5%).

The obtained resin is represented by the following chemical formula (12). Its mass average molecular weight (Mw) was 3100 and the degree of dispersion (MwZMn) was 1.77. Was confirmed by carbon NMR, the composition ratio (mol _^0/0) «was l / m / n = 45/ 45/10. This is referred to as resin 19.

[Formula 22]

Synthetic example 20

 9.1 g of NBHFAA, 6.0 g of AdOHA, 93 g of GBLAO, and 0.7 g of dimethyl azobisisoacetate as a polymerization initiator were dissolved in 200 ml of THF (tetrahydrofuran). Next, this solution was subjected to nitrogen publishing for about 10 minutes, stirred for 4 hours while heating using an oil bath at 70 ° C, and then cooled to room temperature. Next, after the reaction solution was concentrated by an evaporator, the concentrate was dissolved in 200 ml of THF, and poured into 2000 ml of heptane to precipitate a resin, followed by filtration. The obtained resin was dried in a drier at 40 ° C. for 24 hours to obtain 12.4 g of a white solid (yield: 76.9%).

 The obtained resin is represented by the following chemical formula (13). Its mass average molecular weight (Mw) was 3000 and the degree of dispersion (MwZMn) was 1.83.

Was confirmed by carbon NMR, the composition ratio (mol _^0/0) «was l / m / n = 45/ 45/10. This is referred to as resin 20. [0139] [Formula 23]

[0140] Composition (mol%), mass average molecular weight (Mw), dispersion of the resin obtained in Synthesis Examples 13 to 20

 (Mw / Mn) is summarized in Table 5.

[0141] [Table 5] NBHFAA HEM AH AM AdOHA GBLA NBLA Mw Mw / Mn Synthesis example 1 3 42 1 29 29

 (Resin 13) ― ― 6300 1.83 Synthesis example 1 42 29

 (Resin 14) ― 29 ― ― 7500 2.15 Synthesis example 1 5 50 25 ― 25 ― ― 6500 1.92 (Tree finger, 5)

 Synthesis example 1 6 50 ― ― 50 ― ― 3100 1.68 (Resin 16)

 Synthesis example 1 7 40 20 30 10 ― 6000 2.23 (Fiber 17)

 Synthesis example 1 8 40 20 ― 30 1 10 5600 2.24 (Resin 18)

 Synthesis Example 1 9

 (Resin 19) 45 ― 1 45 ― 10 3100 1.77 Synthesis example 20

 (Resin 20) 45 ― ― 45 10 ― 3000 1.83

[Production of resist composition]

 The materials described in Table 6 were mixed to produce negative resist compositions of Examples and Comparative Examples.

[Table 6] (D) Nitrogen-containing

 (A) Resin (B) Acid generator (C) Crosslinker Organic solvent

 Organic compounds

 Resin 1 3 TPS-TF Binderl WW ΠΑ "Zolamine PGME

 Example 1 2

(1 00SS part) (2 trade volume ②) (5 quality a part) (0-4 lending part) (2000 quality S part) Resin 1 4 TPS-TF Binderl Triisov '

Knoll 7 Min

 Example 1 3

 (2 parts S part) (10 parts 3 part)> (0.4¾S part) (2000 parts by mass> resin 7 TPS-TF Binderl Tririf'ar no-Aamine PG E

 Example 14

 (00S parts) (2 parts by mass) (5 parts by mass) (0.4H storage part) (2000 parts by mass)

 ^ 5 TPS-TF Binderl trip ar / -lamine PGME

 Example 1 5

 (100 parts by mass) (2 parts by mass) <5 parts by mass S) (0.4 parts by mass) (2000 parts by mass) Resin 16 TPS-TF Binderl Triirif'U / -le 7min PGME

 Example 16

 (Grade S section) (2 pieces of S section) (5 pieces of storage section) (0.4 parts by mass) (2000 parts by mass) Resin 1 TPS-TF Binderl Triisov 'iw' PGME

 Example 1

<1 00 quality & part) (2 parts by mass) (5 parts by weight of> ^(0.4筲量part) <2000 parts by weight) fttflg l 8 TPS-TF Binderl bird Zoff 'Ο' Breakfast - Le? Min PGME

 Example 18

 <2 parts 8 parts) (5 parts) (0.4 parts by weight) (2000 parts by weight) Resin 19 TPS-TF Binderl type. Λ '/-W Min PGME

 Example 1 S

 (Demand parts> (2K parts) (5 parts) (0.4 parts> (2000 parts) Resin 20 TPS-TF Binderl ΠΛ "-Luamine PGME

 Example 20

<100 parts by mass) (2 parts by weight) (5 parts by weight) ^(0.4 parts by weight) (2000 parts by weight)

[0144] [Evaluation]

 The resolution, pattern shape, and sensitivity were evaluated in the same manner as in the above example except that the conditions at the time of forming the resist pattern were changed to the conditions shown in Table 7 below. Table 8 shows the results.

[0145] [Table 7] Register

 Substrate Anti-reflective coating PAB PEB 腠 Thick

 8 inch AR-19

 Example 1 2 Silicon 200nm 80/60 Qin. C / 60 seconds wafer 82nm

 8 inch AR-19

 Example 1 3 Silicon 200nm 80/60 sec 100 "C / 60sec wafer 82nm

 8 inch AR-19

 Example 1 Silicon 200nm 80. C / 60sec 100 / 60sec wafer 82nm

 8 inch AR-19

 Example 15 5 Silicon 200nm 80Π / 60 sec 100. C / 60 sec ゥ Ah 82nm

 8 inch ARC-29

 Example 16 Silicon / 200 nm 80/60 sec 100/60 sec

 8 inch ARC-29

 Example 17 Silicon 200nm 80 "C / 6Osec 100/60 杪 杪 77nm

 8 inch ARC-29

 Example 1 8 Silicon 200 nm 80/60 sec 100. C / 60 sec.

 8 inch ARC-29

 Example] 9 silicon 2O0nm 80¾ / 60 sec 100. C / 6C second ゥ Aha 77nm

 8 inches

 ARC-29

 Example 20 Silicon 200 nm 80/60 seconds 100/60 seconds

ARC_29 → Product name, organic anti-reflective coating made by Brew Science Inc.

Resolution Pattern shape Sensitivity Example 1 2 1 4 OnmL S 42mJ / cm ² Example 1 3 1 2 OnmL S 29mJ / cm ^e Example 1 4 1 50 rim and S 26mJ / cm ² Example 1 5 1 2 OnmL S 29 mJ / cm ² Example 1 6 1 2 Onm LS ◎ 32 mJ / cm ^a Example 1 7 1 3 OnmL S ◎ 32 mJ / om ² Example 1 8 1 2 OnmL S ◎ 32 mJ / cm ² Example 1 9 1 2 OnmL SO 30mJ / cm ² Example 20 1 3 OnmL S o 35mJ / cm ² From the results shown in Table 8, it was confirmed that in Examples according to the present invention, swelling was suppressed and a fine resist pattern could be formed.

Claims

The scope of the claims

 [1] a structural unit (al) containing an alicyclic group having a fluorinated hydroxyalkyl group;

And a structural unit derived from an acrylate ester, and a structural unit (a2) containing a hydroxyl group-containing alicyclic group.

[2] The resin for a resist composition according to claim 1, wherein a structural unit (al) force is represented by the following general formula:

 The resin for a resist composition represented by (1).

 [Chemical 1]

"2m + 1 ^C n + 1

.. (1)

(Wherein, R is a hydrogen atom, an alkyl group, a fluorinated alkyl group or a fluorine atom, m

, N, and p are each independently an integer of 1 to 5. )

[3] The resin for a resist composition according to claim 1, wherein the alicyclic group of the structural unit (a2) has 5 to 15 carbon atoms.

[4] The resin for a resist composition according to claim 1, wherein the structural unit (a2) has the following general formula (

The resin for a resist composition represented by 2).

[Chemical 2]

(R is a hydrogen atom, an alkyl group, a fluorinated alkyl group or a fluorine atom, and q is an integer of 1-3.)

 [5] The resin for a resist composition according to claim 1, wherein the proportion of the structural unit (al) is 20 to 8

0 mole _^0/0, 榭脂resist composition ratio of 20 to 80 mole _^0/0 structural unit (a2).

[6] The resin for a resist composition according to claim 1, further comprising acrylic acid.

And a structural unit having no cyclic structure and having a structural unit (a3) having an alcoholic hydroxyl group in a side chain.

[7] The resin for a resist composition according to claim 6, wherein the structural unit (a3) force is represented by the following general formula:

 The resin for a resist composition represented by (3).

[Formula 3]

(In the formula, R ¹ is a hydrogen atom, an alkyl group, fluorinated alkyl group, a fluorine atom or a hydroxy Shiarukiru group, R ² represents a hydrogen atom, an alkyl group or hydroxyalkyl group der, is, and, the R ² At least one is a hydroxyalkyl group.)

[8] The resin for a resist composition according to claim 6, wherein the constituent unit (a3) is a a- (hydroxyalkyl) alkyl acrylate ester resin for a resist composition containing a derived constituent unit. .

 [9] The resin for a resist composition according to claim 6, wherein a (a3) force (a-alkyl) hydroxyalkyl acrylate is used for a resist composition containing a derived structural unit. resin.

 [10] The resin for a resist composition according to claim 6, wherein the proportion of the structural unit (al) is 20 to 8

0 mol%, the proportion is 10 to 70 mol% of the structural unit (a2),榭脂resist composition ratio of 10 to 70 mole _^0/0 structural unit (a3).

[11] The resin for a resist composition according to claim 1, further comprising a structural unit (a4) derived from an acrylate ester containing a rataton-containing monocyclic or polycyclic group. .

 [12] The resin for a resist composition according to the resin for a resist composition according to claim 11, further comprising: a constituent unit (a4) a constituent unit derived from an acrylate ester containing norbornane lactone.

 [13] The resin for a resist composition according to claim 11, wherein the proportion of the structural unit (al) is from 20 to

85 mol%, proportion 14-70 mole% of the structural unit (a2),榭脂resist composition ratio of 1 to 70 mol _^0/0 structural unit (a4).

[14] The resin for a resist composition according to claim 6, further comprising a structural unit (a4) derived from an acrylate ester containing a rataton-containing monocyclic or polycyclic group.

 15. The resin for a resist composition according to claim 14, wherein the structural unit (a4) includes a structural unit derived from an acrylate ester containing norbornane ratatone.

[16] The resin for a resist composition according to claim 14, wherein the proportion of the structural unit (al) is from 10 to 85 mol%, the ratio 10 to 80 mol% of the structural unit (a2), the proportion force 70 mole _^0/0 of the structural unit (a3), is in a proportion force ^ to 70 mole _^0/0 of the structural unit (a4) Resins for resist compositions.

[17] The resin for a resist composition according to claim 11, wherein the structural unit (a4) is a structural unit having a hydrogen atom bonded to the oc position.

[18] The resin for a resist composition according to claim 14, wherein the structural unit (a4) is a structural unit having a hydrogen atom bonded to the _α- position.

[19] The resin for a resist composition according to claim 2, wherein R in the general formula (1) is a hydrogen atom.

[20] The resin for a resist composition according to claim 1, wherein

 The structural unit (a2) is a resin for a resist composition, which is a structural unit formed by bonding a hydrogen atom to the oc position.

 [21] The resin for a resist composition according to claim 1, wherein the weight average molecular weight is from 2000 to 30.

A resin for a resist composition in the range of 000.

[22] A negative type comprising (A) the resin for a resist composition according to claim 1, (B) an acid generator component that generates an acid upon exposure, and (C) a crosslinking agent component. Resist composition.

23. The negative resist composition according to claim 22, wherein the component (B) is a potassium salt having a fluorinated alkyl sulfonate ion as an ion.

[24] The negative resist composition according to claim 22, wherein the component (C) is a melamine-based crosslinking agent.

A negative resist composition which is at least one selected from a urea-based crosslinking agent, an ethylene-urea-based crosslinking agent, and a glycol-peryl-based crosslinking agent.

[25] The negative resist composition according to claim 22, further comprising a nitrogen-containing organic compound.

26. The negative resist composition according to claim 22, which is for a process using an ArF excimer laser as an exposure light source.

[27] The negative resist composition according to any one of claims 22 to 26 is applied on a substrate.

A pre-beta, selectively exposing, subjecting to PEB (post-exposure baking), and alkali developing to form a resist pattern.