JP5461598B2 - Resin resin - Google Patents

Description

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

In lithography technology, for example, a resist film made of a resist material is formed on a substrate, and the resist film is selectively exposed to light such as light or an electron beam through a mask on which a predetermined pattern is formed. And a development process is performed to form a resist pattern having a predetermined shape on the resist film.
A resist material in which the exposed portion changes to a property that dissolves in the developer is referred to as a positive type, and a resist material that changes to a property in which the exposed portion does not dissolve in the developer is referred to as a negative type.
In recent years, in the manufacture of semiconductor elements and liquid crystal display elements, pattern miniaturization has been rapidly progressing due to advances in lithography technology.
As a technique for miniaturization, the wavelength of an exposure light source is generally shortened. Specifically, conventionally, ultraviolet rays typified by g-line and i-line have been used, but at present, mass production of semiconductor elements using a KrF excimer laser or an ArF excimer laser has started.
In addition, studies have been made on F ₂ excimer lasers, electron beams, EUV (extreme ultraviolet rays), X-rays, and the like having shorter wavelengths than these excimer lasers.

Resist materials are required to have lithography characteristics such as sensitivity to these exposure light sources and resolution capable of reproducing a pattern with fine dimensions.
As a resist material satisfying such requirements, a chemically amplified resist containing a base resin whose alkali solubility is changed by the action of an acid and an acid generator that generates an acid upon exposure is used.
For example, a positive chemically amplified resist contains, as a base resin, a resin component that has an acid dissociable, dissolution-inhibiting group, increases alkali solubility by the action of an acid, and an acid generator. Sometimes, when an acid is generated from the acid generator by exposure, the exposed portion becomes alkali-soluble.
On the other hand, a negative chemically amplified resist contains, for example, a resin component having a carboxy group, a crosslinking agent having an alcoholic hydroxyl group, and an acid generator, and the acid generated from the acid generator at the time of resist pattern formation. By the action, the resin component changes from alkali-soluble to insoluble by reacting the carboxy group of the resin component with the alcoholic hydroxyl group of the crosslinking agent.
At present, as a resist base resin used in ArF excimer laser lithography and the like, since it is excellent in transparency near 193 nm, a resin having a structural unit derived from (meth) acrylate ester (acrylic) And the like are generally used (see, for example, Patent Document 1).

JP 2003-241385 A

In the future, it will be required to provide a new resist material in response to demands for various lithography properties such as higher resolution.
The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a novel resin, a resist composition using the resin, and a resist pattern forming method using the resist composition.

The present inventors propose the following means in order to solve the above problems.
That is, the resist resin of the present invention includes a structural unit (a0) represented by the following general formula (a-0) and a structural unit (a1) derived from an acrylate ester containing an acid dissociable, dissolution inhibiting group. And the alkali solubility is increased by the action of an acid.

［式中、Ｒは水素原子、ハロゲン原子、炭素原子数１〜５のアルキル基または炭素原子数１〜５のハロゲン化アルキル基を表し；ａは０〜２の整数であり；ｂは１〜３の整数であり；ｃは１〜２の整数であり；ａ＋ｂは２以上の整数である。］

[Wherein, R represents a hydrogen atom, a halogen atom, a halogen Kaa alkyl group of 1 to 5 alkyl groups or carbon atoms of 1 to 5 carbon atoms; a is an integer from 0 to 2; b is 1 C is an integer of 3; c is an integer of 1 to 2; a + b is an integer of 2 or more. ]

In the present specification and claims, the “base resin component (A)” refers to a resin component whose alkali solubility changes due to the action of an acid, and a resin component ( A ′) and an alkali-soluble resin component (A ″).
“Exposure” is a concept including general irradiation of radiation.

  According to the present invention, a novel resin, a resist composition using the resin, and a resist pattern forming method using the resist composition can be provided.

≪Resist composition≫
The resist composition of the present invention comprises a base resin component (A) (hereinafter referred to as (A) component) and an acid generator component (B) that generates acid upon exposure (hereinafter referred to as (B) component). Containing.
The component (A) includes a resin (A1) having a structural unit (a0) represented by the general formula (a-0).
In the resin (A1), the proportion of the structural unit (a0) is preferably 10 to 100 mol%, more preferably 15 to 100 mol%, based on all the structural units constituting the resin (A1). More preferably, it is 20-100 mol%. By setting it to the lower limit value or more, a pattern can be obtained when the resist composition is formed, and the effect of including the structural unit (a0) can be sufficiently obtained.
The component (A) is preferably a resin component (A ′) (hereinafter referred to as component (A ′)) whose alkali solubility is increased by the action of an acid. The resist composition containing the component (A ′) is a so-called positive resist composition.
In the resist composition of the present invention, preferably, the component (A) is an alkali-soluble resin component (A ″) (hereinafter referred to as (A ″) component), and further a crosslinking agent component (C) (hereinafter referred to as “Cross-linking agent component”). And (C) component). The resist composition becomes a so-called negative resist composition.
Hereinafter, each of the positive resist composition and the negative resist composition will be described in detail.

(Positive resist composition)
The positive resist composition in the present invention contains the component (A ′) and the component (B).
In such a positive resist composition, the component (A ′) is insoluble in alkali before exposure, and when an acid generated from the component (B) acts upon exposure, the acid dissociable, dissolution inhibiting group is dissociated, thereby (A ') The alkali solubility of the whole component increases and changes from alkali-insoluble to alkali-soluble. Therefore, when a resist film obtained by using a positive resist composition is selectively exposed in the formation of a resist pattern, the exposed portion turns alkali-soluble, while the unexposed portion remains alkali-insoluble. Therefore, alkali development can be performed.

<(A ') component>
In such a positive resist composition, the component (A ′) includes a resin (A1) having the structural unit (a0) represented by the general formula (a-0).
Preferably, the resin (A1) further has a structural unit (a1) derived from an acrylate ester containing an acid dissociable, dissolution inhibiting group.
Preferably, the resin (A1) further has a structural unit (a3) derived from an acrylate ester containing a polar group-containing aliphatic hydrocarbon group, which does not correspond to the structural unit (a0).

Here, in the present specification and claims, the “structural unit derived from an acrylate ester” means a structural unit formed by cleavage of an ethylenic double bond of an acrylate ester.
“Acrylic acid esters” include those in which a hydrogen atom is bonded to the carbon atom at the α-position, and those in which a substituent (atom or group other than a hydrogen atom) is bonded to the carbon atom in the α-position. Include concepts. Examples of the substituent include a halogen atom, a lower alkyl group, and a halogenated lower alkyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is particularly preferable.
The α-position (α-position carbon atom) of a structural unit derived from an acrylate ester is a carbon atom to which a carbonyl group is bonded unless otherwise specified.
Unless otherwise specified, the “alkyl group” includes linear, branched and cyclic monovalent saturated hydrocarbon groups.
The “lower alkyl group” is an alkyl group having 1 to 5 carbon atoms.
In the acrylate ester, as the lower alkyl group as a substituent at the α-position, specifically, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, Examples include lower linear or branched alkyl groups such as isopentyl group and neopentyl group.
In the present invention, the α-position of the acrylate ester is preferably a hydrogen atom, a halogen atom, a lower alkyl group or a halogenated lower alkyl group, and a hydrogen atom, a fluorine atom, a lower alkyl group or a fluorine atom. A lower alkyl group is more preferable, and a hydrogen atom or a methyl group is most preferable in terms of industrial availability.

・ Structural unit (a0)
The resin (A1) includes a structural unit (a0) represented by the general formula (a-0). A positive resist composition using the resin (A1) can form a resist pattern. Further, when the resin (A1) contains the structural unit (a0), the effect of increasing the adhesion of the resist film to the substrate and the hydrophilicity with the developer can be obtained, and the structural unit (a2) described later. The same effect can be obtained.

In the general formula (a-0), R represents a hydrogen atom, a halogen atom, a lower alkyl group, or a halogenated lower alkyl group. The halogen atom, lower alkyl group or halogenated lower alkyl group is the same as the halogen atom, lower alkyl group or halogenated lower alkyl group which may be bonded to the α-position of the acrylate ester. R is most preferably a methyl group.
In the general formula (a-0), a is an integer of 0 to 2, and preferably 1.
B is an integer of 1 to 3, and is preferably 2.
C is an integer of 1 to 2, preferably 1.
Moreover, a + b is an integer greater than or equal to 2, Preferably it is 2-4, Most preferably, it is 3.
The substitution position of the hydroxyl group may be any position when c is 1. In particular, it is desirable to bond to the carbon atom adjacent to the carbon atom bonded to the terminal oxygen atom of -C (O) -O-. Furthermore, when c is 2, arbitrary substitution positions can be combined.

  Specific examples of preferred structural units as the structural unit (a0) are shown below.

Among these, 3-methacryloyloxy-4-hydroxytetrahydrofuran represented by the chemical formula (a0-1) and 3-acryloyloxy-4-hydroxytetrahydrofuran represented by the chemical formula (a0-2) are particularly preferable, and the chemical formula (a0 Most preferred is 3-methacryloyloxy-4-hydroxytetrahydrofuran represented by -1).
In the resin (A1) contained in the positive resist composition, as the structural unit (a0), one type of structural unit may be used alone, or two or more types may be used in combination.
The proportion of the structural unit (a0) in the resin (A1) is preferably 10 to 70 mol%, more preferably 10 to 60 mol%, based on the total of all structural units constituting the resin (A1). More preferred is ˜55 mol%. By setting it to the lower limit value or more, the effect of containing the structural unit (a0) can be sufficiently obtained, and by setting the upper limit value or less, it is possible to balance with other structural units.

The monomer for deriving the structural unit (a0) can be produced by the following method.
(1) Synthesis of monomers represented by the above chemical formulas (a0-1) and (a0-2) cis-3,4-dihydroxytetrahydrofuran in the presence of an organic base such as triethylamine or pyridine or an inorganic base such as sodium carbonate; By reacting with an equivalent amount of methacryloyl chloride or acryloyl chloride, monomers corresponding to the chemical formulas (a0-1) and (a0-2) can be produced, respectively. Moreover, the corresponding acid anhydride can also be used instead of said acid chloride.
Furthermore, the target monomer can be produced by the reaction of erythritan and methacrylic acid or acrylic acid in the presence of dicyclohexylcarbodiimide.
(2) Synthesis of monomers represented by the chemical formulas (a0-3) and (a0-4) As shown in the following examples, the target product can be produced by using a known method. For example, C.I. Andre, J .; Bolte, C.I. Demuynck, Tetrahedron Asymmetry, vol. 9, p. 1359 (1998), 3,4-dihydroxybutanal was obtained using 2,2-dimethyl-1,3-dioxolane-4-ethyl acetate as a raw material, Monet, M .; Schlosser, Tetrahedron Letters, vol. 25, p. 4491 (1984) is used to lead to tetrahydro-2,4-furandol.
Next, for example, P.I. Hadwiger, A .; E. Stuetz, Journal of Carbohydrates Chemistry, vol. 17, p. 1259 (1998) to obtain tetrahydro-2,4-furande (meth) acrylate. Finally, it is treated with ammonia (see, for example, L.N. Lysenkova, M.I. Reznikova, A.M. Korolev, M.N. Thus, the target monomer can be produced.
(3) Synthesis of monomers represented by the chemical formulas (a0-5) and (a0-6) The intermediate tetrahydro-2,4-furandol described above can be derived as a raw material. For example, the target product can be produced by reacting 1 equivalent of acryloyl chloride or methacryloyl chloride in the presence of 1 equivalent of an organic amine.

・ Structural unit (a1)
In the present invention, the resin (A1) preferably further has a structural unit (a1) derived from an acrylate ester containing an acid dissociable, dissolution inhibiting group.
The acid dissociable, dissolution inhibiting group in the structural unit (a1) has an alkali dissolution inhibiting property that makes the entire resin (A1) insoluble in alkali before dissociation, and changes the entire resin (A1) to alkali-soluble after dissociation. If it is a thing, the thing proposed until now as an acid dissociable, dissolution inhibiting group of the base resin for chemically amplified resists can be used. Generally, a group that forms a cyclic or chain tertiary alkyl ester with a carboxy group of (meth) acrylic acid, or a group that forms a cyclic or chain alkoxyalkyl ester is widely known. . The “(meth) acrylic acid ester” means one or both of an acrylic acid ester having a hydrogen atom bonded to the α-position and a methacrylic acid ester having a methyl group bonded to the α-position.

Here, the tertiary alkyl ester is an ester formed by replacing the hydrogen atom of a carboxy group with a chain or cyclic alkyl group, and the carbonyloxy group (—C (O) —O). The structure in which the tertiary carbon atom of the chain or cyclic alkyl group is bonded to the oxygen atom at the terminal of-). In this tertiary alkyl ester, when an acid acts, a bond is cut between an oxygen atom and a tertiary carbon atom.
The chain or cyclic alkyl group may have a substituent.
Hereinafter, a group that is acid dissociable by constituting a carboxy group and a tertiary alkyl ester is referred to as a “tertiary alkyl ester type acid dissociable, dissolution inhibiting group” for convenience.
The cyclic or chain alkoxyalkyl ester forms an ester by replacing the hydrogen atom of the carboxy group with an alkoxyalkyl group, and the carbonyloxy group (—C (O) —O—) A structure in which the alkoxyalkyl group is bonded to a terminal oxygen atom is shown. In this alkoxyalkyl ester, when an acid acts, a bond is cut between an oxygen atom and an alkoxyalkyl group.

  As the structural unit (a1), one type selected from the group consisting of structural units represented by general formula (a1-0-1) shown below and structural units represented by general formula (a1-0-2) shown below. It is preferable to use the above.

（式中、Ｒは水素原子、ハロゲン原子、低級アルキル基またはハロゲン化低級アルキル基を示し；Ｘ^１は酸解離性溶解抑制基を示す。）

(In the formula, R represents a hydrogen atom, a halogen atom, a lower alkyl group or a halogenated lower alkyl group; X ¹ represents an acid dissociable, dissolution inhibiting group.)

（式中、Ｒは水素原子、ハロゲン原子、低級アルキル基またはハロゲン化低級アルキル基を示し；Ｘ^２は酸解離性溶解抑制基を示し；Ｙ^２はアルキレン基または脂肪族環式基を示す。）

(Wherein R represents a hydrogen atom, a halogen atom, a lower alkyl group or a halogenated lower alkyl group; X ² represents an acid dissociable, dissolution inhibiting group; Y ² represents an alkylene group or an aliphatic cyclic group. )

In the general formula (a1-0-1), the halogen atom, lower alkyl group or halogenated lower alkyl group of R is a halogen atom, lower alkyl group or halogenated lower group which may be bonded to the α-position of the acrylate ester. It is the same as the alkyl group. R is most preferably a methyl group.
X ¹ is not particularly limited as long as it is an acid dissociable, dissolution inhibiting group, and examples thereof include an alkoxyalkyl group, a tertiary alkyl ester type acid dissociable, dissolution inhibiting group, and the like. Acid dissociable, dissolution inhibiting groups are preferred. Examples of the tertiary alkyl ester type acid dissociable, dissolution inhibiting group include an aliphatic branched acid dissociable, dissolution inhibiting group and an acid dissociable, dissolution inhibiting group containing an aliphatic cyclic group.
Here, “aliphatic” in the claims and the specification is a relative concept with respect to aromatics, and is defined to mean groups, compounds, and the like that do not have aromaticity. The “aliphatic cyclic group” means a monocyclic group or a polycyclic group having no aromaticity.
The “aliphatic cyclic group” in the structural unit (a1) may or may not have a substituent. Examples of the substituent include a lower alkyl group having 1 to 5 carbon atoms, a fluorine atom, a fluorinated lower alkyl group having 1 to 5 carbon atoms substituted with a fluorine atom, an oxygen atom (= O), and the like.
The basic ring structure excluding the substituent of the “aliphatic cyclic group” is not limited to a group consisting of carbon and hydrogen (hydrocarbon group), but is preferably a hydrocarbon group. The “hydrocarbon group” may be either saturated or unsaturated, but is usually preferably saturated. A polycyclic group is preferred.
Specific examples of such aliphatic cyclic groups include, for example, monocycloalkanes, bicycloalkanes, trialkyls which may or may not be substituted with a lower alkyl group, a fluorine atom or a fluorinated alkyl group. Examples include groups in which one or more hydrogen atoms have been removed from a polycycloalkane such as cycloalkane or tetracycloalkane. Specific examples include monocycloalkanes such as cyclopentane and cyclohexane, and groups obtained by removing one or more hydrogen atoms from polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.
Specific examples of the aliphatic branched acid dissociable, dissolution inhibiting group include a tert-butyl group and a tert-amyl group.
Examples of the acid dissociable, dissolution inhibiting group containing an aliphatic cyclic group include a group having a tertiary carbon atom on the ring skeleton of a cyclic alkyl group, specifically 2-methyl Examples include a 2-adamantyl group and a 2-ethyl-2-adamantyl group. Alternatively, as a structural unit represented by the following general formula, a group having an aliphatic cyclic group such as an adamantyl group and a branched alkylene group having a tertiary carbon atom bonded thereto can be given.

［式中、Ｒは上記と同じであり、Ｒ^１５、Ｒ^１６はアルキル基（直鎖、分岐鎖状のいずれでもよく、好ましくは炭素数１〜５である。）を示す。］

[Wherein, R is the same as described above, and R ¹⁵ and R ^{16 each} represents an alkyl group (which may be linear or branched, and preferably has 1 to 5 carbon atoms). ]

  Further, the alkoxyalkyl group is preferably a group represented by the following general formula.

（式中、Ｒ^１７、Ｒ^１８はそれぞれ独立して直鎖状または分岐状のアルキル基または水素原子であり、Ｒ^１９は直鎖状、分岐状または環状のアルキル基である。または、Ｒ^１７とＲ^１９の末端が結合して環を形成していてもよい。）

(Wherein R ¹⁷ and R ¹⁸ are each independently a linear or branched alkyl group or a hydrogen atom, and R ¹⁹ is a linear, branched or cyclic alkyl group, or R ^17. And the end of R ¹⁹ may be bonded to form a ring.)

In R ¹⁷ and R ¹⁸ , the alkyl group preferably has 1 to 15 carbon atoms, may be linear or branched, and is preferably an ethyl group or a methyl group, and most preferably a methyl group. In particular, it is preferable that one of R ¹⁷ and R ¹⁸ is a hydrogen atom and the other is a methyl group.
R ¹⁹ is a linear, branched or cyclic alkyl group, preferably having 1 to 15 carbon atoms, and may be linear, branched or cyclic.
When R ¹⁹ is linear or branched, it preferably has 1 to 5 carbon atoms, more preferably an ethyl group or a methyl group, and most preferably an ethyl group.
When R ¹⁹ is cyclic, it preferably has 4 to 15 carbon atoms, more preferably 4 to 12 carbon atoms, and most preferably 5 to 10 carbon atoms. Specifically, one or more polycycloalkanes such as monocycloalkane, bicycloalkane, tricycloalkane, and tetracycloalkane, which may or may not be substituted with a fluorine atom or a fluorinated alkyl group, are included. Examples include a group excluding a hydrogen atom. Specific examples include monocycloalkanes such as cyclopentane and cyclohexane, and groups obtained by removing one or more hydrogen atoms from polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. Among them, a group obtained by removing one or more hydrogen atoms from adamantane is preferable.
In the above formula, R ¹⁷ and R ¹⁹ are each independently an alkylene group having 1 to 5 carbon atoms, and the end of R ^{19 and} the end of R ¹⁷ may be bonded to each other.
In this case, a cyclic group is formed by R ¹⁷ , R ¹⁹ , the oxygen atom to which R ¹⁹ is bonded, and the carbon atom to which the oxygen atom and R ¹⁷ are bonded. The cyclic group is preferably a 4- to 7-membered ring, and more preferably a 4- to 6-membered ring. Specific examples of the cyclic group include a tetrahydropyranyl group and a tetrahydrofuranyl group.

In general formula (a1-0-2), R is the same as defined above. X ² is the same as X ¹ in formula (a1-0-1).
Y ² is preferably an alkylene group having 1 to 4 carbon atoms or a divalent aliphatic cyclic group.
When Y ² is a divalent aliphatic cyclic group, Y ² is an explanation of the “aliphatic cyclic group” in the structural unit (a1) except that a group in which two or more hydrogen atoms are removed is used. Similar ones can be used.

  More specifically, examples of the structural unit (a1) include structural units represented by the following general formulas (a1-1) to (a1-4).

［上記式中、Ｘ’は第３級アルキルエステル型酸解離性溶解抑制基を表し、Ｙは炭素数１〜５の低級アルキル基、または脂肪族環式基を表し；ｎは０〜３の整数を表し；ｍは０または１を表し；Ｒは前記と同じであり、Ｒ^１’、Ｒ^２’はそれぞれ独立して水素原子または炭素数１〜５の低級アルキル基を表す。］

[In the above formula, X ′ represents a tertiary alkyl ester type acid dissociable, dissolution inhibiting group, Y represents a lower alkyl group having 1 to 5 carbon atoms, or an aliphatic cyclic group; M represents 0 or 1; R is the same as defined above; R ¹ ′ and R ² ′ each independently represent a hydrogen atom or a lower alkyl group having 1 to 5 carbon atoms. ]

In the R ¹ ′ and R ² ′, at least one is preferably a hydrogen atom, and more preferably both are hydrogen atoms. n is preferably 0 or 1.

X ′ is the same as the tertiary alkyl ester type acid dissociable, dissolution inhibiting group exemplified in X ¹ above.
Examples of the aliphatic cyclic group for Y include the same groups as those exemplified above in the description of “aliphatic cyclic group”.

  Specific examples of the structural units represented by the general formulas (a1-1) to (a1-4) are shown below.

In the resin (A1) contained in the positive resist composition, as the structural unit (a1), one type may be used alone, or two or more types may be used in combination.
Among these, the structural unit represented by the general formula (a1-1), the structural unit represented by (a1-3), and the structural unit represented by (a1-4) are preferable. a1-1-1) to (a1-1-6), formulas (a1-1-35) to (a1-1-43), formulas (a1-3-17) to (a1-3-24) and formulas It is preferable to use at least one selected from structural units represented by (a1-4-9) to (a1-4-10).
Further, as the structural unit (a1), since the resist pattern shape is good, the following general formula (a1-1-01) including the structural units of the formulas (a1-1-1) to (a1-1-4) is included. ) Is particularly preferred.
Further, since the mask error factor (MEF) is good, it is represented by the following general formula (a1-1-02) including the structural units of the formulas (a1-1-35) to (a1-1-41). Those are also particularly preferred.
Note that "MEF" can faithfully reproduce mask patterns of different sizes when the mask size (line width in a line-and-space pattern) is changed with the same exposure amount and a fixed pitch. The closer the MEF value is to 1, the better the mask reproducibility.
Furthermore, the following general formula (a1-1-04) and formula (a1-4-) including the structural units of the formula (a1-1-03) and the formulas (a1-3-17) to (a1-3-24) Those represented by the following general formula (a1-1-05) including the structural units 9) to (a1-4-10) are also particularly preferable.

（式中、Ｒは水素原子、ハロゲン原子、低級アルキル基またはハロゲン化低級アルキル基を示し、Ｒ^１１は低級アルキル基を示す。）

(In the formula, R represents a hydrogen atom, a halogen atom, a lower alkyl group or a halogenated lower alkyl group, and R ¹¹ represents a lower alkyl group.)

（式中、Ｒは前記と同じであり、Ｒ^１２は低級アルキル基を示す。ｈは１〜３の整数を表す。）

(In the formula, R is the same as described above, R ¹² represents a lower alkyl group, and h represents an integer of 1 to 3.)

（式中、Ｒは前記と同じである。）

(In the formula, R is as defined above.)

（式中、Ｒ、Ｒ^１２、ｍ、ｈは前記と同じである。）

(In the formula, R, R ¹² , m and h are the same as described above.)

（式中、Ｒ、ｍ、ｎ、ｈは前記と同じである。）

(In the formula, R, m, n and h are the same as above.)

In general formula (a1-1-01), R is the same as defined above. The lower alkyl group for R ^{11 is the same as} the lower alkyl group for R, and is preferably a methyl group or an ethyl group.
In general formula (a1-1-02), R is the same as defined above. The lower alkyl group for R ^{12 is the same as} the lower alkyl group for R, preferably a methyl group or an ethyl group, and most preferably an ethyl group. h is preferably 1 or 2, and most preferably 2.
In general formula (a1-1-03), R is the same as defined above.
In general formula (a1-1-04), R is the same as described above. R ¹² is the same as described above, and most preferably a methyl group. h is preferably 1 or 2, and most preferably 1. m is preferably 0.
In general formula (a1-1-05), R is the same as defined above. h is preferably 1 or 2, and most preferably 2. m is preferably 0. n is preferably 0 or 1, and more preferably 0.

  In the resin (A1), the proportion of the structural unit (a1) is preferably 10 to 80 mol%, more preferably 15 to 70 mol%, and more preferably 15 to 50 mol% with respect to all the structural units constituting the resin (A1). Is more preferable. By setting it to the lower limit value or more, a pattern can be obtained when the resist composition is used, and by setting it to the upper limit value or less, it is possible to balance with other structural units.

・ Structural unit (a3)
In the present invention, the resin (A1) preferably further includes a structural unit (a3) derived from an acrylate ester containing a polar group-containing aliphatic hydrocarbon group, which does not correspond to the structural unit (a0). . By having the structural unit (a3), the hydrophilicity of the component (A) is increased, the affinity with the developer is increased, the alkali solubility in the exposed area is further improved, and the resolution is improved. .
Examples of the polar group include a hydroxyl group, a cyano group, a carboxy group, and a hydroxyalkyl group in which a part of hydrogen atoms of an alkyl group is substituted with a fluorine atom. A hydroxyl group is particularly preferable.
Examples of the aliphatic hydrocarbon group include a linear or branched hydrocarbon group having 1 to 10 carbon atoms (preferably an alkylene group) and a polycyclic aliphatic hydrocarbon group (polycyclic group). . As the polycyclic group, for example, a resin for a resist composition for ArF excimer laser can be appropriately selected from among many proposed ones.
Among them, a structural unit derived from an acrylate ester containing an aliphatic polycyclic group containing a hydroxyalkyl group in which a part of hydrogen atoms of a hydroxyl group, a cyano group, a carboxy group, or an alkyl group is substituted with a fluorine atom Is more preferable. Examples of the polycyclic group include groups in which one or more hydrogen atoms have been removed from bicycloalkane, tricycloalkane, tetracycloalkane, or the like. Specific examples include groups in which one or more hydrogen atoms have been removed from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane, or tetracyclododecane. Among these polycyclic groups, there are groups in which two or more hydrogen atoms have been removed from adamantane, groups in which two or more hydrogen atoms have been removed from norbornane, and groups in which two or more hydrogen atoms have been removed from tetracyclododecane. Industrially preferable.

  The structural unit (a3) is derived from a hydroxyethyl ester of acrylic acid when the hydrocarbon group in the polar group-containing aliphatic hydrocarbon group is a linear or branched hydrocarbon group having 1 to 10 carbon atoms. When the hydrocarbon group is a polycyclic group, the structural unit represented by the following formula (a3-1), the structural unit represented by the following formula (a3-2), the following formula ( The structural unit represented by a3-3) is preferred.

（式中、Ｒは前記に同じであり、ｊは１〜３の整数であり、ｋは１〜３の整数であり、ｔ’は１〜３の整数であり、ｌは１〜５の整数であり、ｓは１〜３の整数である。）

(Wherein R is the same as above, j is an integer of 1 to 3, k is an integer of 1 to 3, t 'is an integer of 1 to 3, and l is an integer of 1 to 5) And s is an integer of 1 to 3.)

In formula (a3-1), j is preferably 1 or 2, and more preferably 1. When j is 2, it is preferable that the hydroxyl group is bonded to the 3rd and 5th positions of the adamantyl group. When j is 1, it is preferable that the hydroxyl group is bonded to the 3-position of the adamantyl group.
j is preferably 1, and a hydroxyl group bonded to the 3rd position of the adamantyl group is particularly preferred.

  In formula (a3-2), k is preferably 1. The cyano group is preferably bonded to the 5th or 6th position of the norbornyl group.

  In formula (a3-3), t ′ is preferably 1. l is preferably 1. s is preferably 1. These preferably have a 2-norbornyl group or a 3-norbornyl group bonded to the terminal of the carboxy group of acrylic acid. The fluorinated alkyl alcohol is preferably bonded to the 5th or 6th position of the norbornyl group.

In the resin (A1) contained in the positive resist composition, as the structural unit (a3), one type of structural unit may be used alone, or two or more types may be used in combination.
In the resin (A1), the proportion of the structural unit (a3) is preferably 5 to 50 mol%, more preferably 5 to 40 mol%, based on all the structural units constituting the resin (A1). 5-25 mol% is more preferable.

・ Structural unit (a2)
In the present invention, the resin (A1) may further have a structural unit (a2) derived from an acrylate ester containing a lactone-containing cyclic group.
Here, the lactone-containing cyclic group refers to a cyclic group containing one ring (lactone ring) containing an —O—C (O) — structure. The lactone ring is counted as the first ring, and when it is only the lactone ring, it is called a monocyclic group, and when it has another ring structure, it is called a polycyclic group regardless of the structure.
The lactone cyclic group of the structural unit (a2) improves the adhesion of the resist film to the substrate and the hydrophilicity with the developer when the resin (A1) is used for forming a resist film. It is effective.

As the structural unit (a2), any unit can be used without any particular limitation.
Specifically, examples of the lactone-containing monocyclic group include groups in which one hydrogen atom has been removed from γ-butyrolactone. Examples of the lactone-containing polycyclic group include groups in which one hydrogen atom has been removed from a bicycloalkane, tricycloalkane, or tetracycloalkane having a lactone ring.

  More specifically, examples of the structural unit (a2) include structural units represented by general formulas (a2-1) to (a2-5) shown below.

［式中、Ｒは前記と同じであり、Ｒ’は水素原子、低級アルキル基、または炭素数１〜５のアルコキシ基であり、ｍは０または１の整数である。Ａは炭素数１〜５のアルキレン基または酸素原子である。］

[Wherein, R is the same as defined above, R ′ is a hydrogen atom, a lower alkyl group, or an alkoxy group having 1 to 5 carbon atoms, and m is an integer of 0 or 1.] A is an alkylene group having 1 to 5 carbon atoms or an oxygen atom. ]

R in the general formulas (a2-1) to (a2-5) is the same as R.
The lower alkyl group for R ′ is the same as the lower alkyl group for R.
In general formulas (a2-1) to (a2-5), R ′ is preferably a hydrogen atom in view of industrial availability.
Specific examples of the alkylene group having 1 to 5 carbon atoms of A include a methylene group, an ethylene group, an n-propylene group, and an isopropylene group.
Below, the specific structural unit of the said general formula (a2-1)-(a2-5) is illustrated.

  Among these, it is preferable to use at least one selected from general formulas (a2-1) to (a2-5), and at least one selected from general formulas (a2-1) to (a2-3). It is preferable to use more than one species. Specifically, chemical formulas (a2-1-1), (a2-1-2), (a2-2-1), (a2-2-2), (a2-3-1), (a2-3) -2), at least one selected from (a2-3-9) and (a2-3-10) is preferably used.

In the resin (A1) contained in the positive resist composition, as the structural unit (a2), one type may be used alone, or two or more types may be used in combination.
When the resin (A1) contains the structural unit (a2), the proportion of the structural unit (a2) is 5 to 60 mol% with respect to the total of all the structural units constituting the resin (A1). Preferably, 10-50 mol% is more preferable, and 20-50 mol% is further more preferable. By making it the lower limit value or more, the effect of containing the structural unit (a2) can be sufficiently obtained, and by making it the upper limit value or less, it is possible to balance with other structural units.

・ Structural unit (a4)
The resin (A1) may contain other structural units (a4) other than the structural units (a0) and (a1) to (a3) as long as the effects of the present invention are not impaired.
The structural unit (a4) is not particularly limited as long as it is another structural unit not classified into the above structural units (a0) and (a1) to (a3), and is preferably used for ArF excimer laser and KrF excimer laser (preferably Can be used for many resists conventionally used as resist resins such as ArF excimer laser).
As the structural unit (a4), for example, a structural unit derived from an acrylate ester containing a non-acid-dissociable aliphatic polycyclic group is preferable. Examples of the polycyclic group include those exemplified in the case of the structural unit (a1), and for ArF excimer laser and KrF excimer laser (preferably for ArF excimer laser). A number of hitherto known materials can be used as the resin component of the resist composition.
In particular, at least one selected from a tricyclodecanyl group, an adamantyl group, a tetracyclododecanyl group, an isobornyl group, and a norbornyl group is preferable in terms of industrial availability. These polycyclic groups may be substituted with a linear or branched alkyl group having 1 to 5 carbon atoms.
Specific examples of the structural unit (a4) include those represented by the following general formulas (a4-1) to (a4-5).

（式中、Ｒは前記と同じである。）

(In the formula, R is as defined above.)

  When the structural unit (a4) is contained in the resin (A1), the structural unit (a4) is contained in an amount of 1 to 30 mol%, preferably 10 to 10% with respect to the total of all the structural units constituting the resin (A1). It is preferable to contain 20 mol%.

In the positive resist composition of the present invention, the resin (A1) is a resin having at least the structural unit (a0), preferably a resin further having the structural unit (a1) and / or (a3).
Examples of such a resin include a copolymer having structural units (a0), (a1) and (a3), a copolymer having structural units (a0) and (a1), and other structural units in these structural units. And a copolymer having the same.
Examples of such copolymers include copolymers composed of the structural units (a0), (a1) and (a3), copolymers composed of the structural units (a0), (a1) and (a2), and the like. it can.
In the positive resist composition of the present invention, the resin (A1) preferably includes a combination of structural units such as the following formulas (A1-11) to (A1-16).

［式中、Ｒ、Ｒ^１１は前記と同じである。］

[Wherein, R and R ¹¹ are the same as defined above. ]

［式中、Ｒ、Ｒ^１２、ｍ、ｈは前記と同じである。］

[Wherein, R, R ¹² , m and h are the same as defined above. ]

［式中、Ｒ、Ｒ^１２、ｈは前記と同じである。］

[Wherein, R, R ¹² and h are the same as defined above. ]

［式中、Ｒ、ｍ、ｎ、ｈは前記と同じである。］

[Wherein, R, m, n and h are the same as defined above. ]

［式中、Ｒ、Ｒ^１２、ｈは前記と同じである。］

[Wherein, R, R ¹² and h are the same as defined above. ]

［式中、Ｒは前記と同じである。］

[Wherein, R is the same as defined above. ]

The mass average molecular weight (Mw) of the resin (A1) contained in the positive resist composition (polystyrene conversion standard by gel permeation chromatography) is not particularly limited, but preferably 2000 to 50000, 3000 to 30000. Is more preferable, and 5000 to 20000 is most preferable. If it is smaller than the upper limit of this range, there is sufficient solubility in a resist solvent to be used as a resist, and if it is larger than the lower limit of this range, dry etching resistance and resist pattern cross-sectional shape are good.
Further, the dispersity (Mw / Mn) is preferably 1.0 to 5.0, more preferably 1.0 to 3.0, and most preferably 1.2 to 2.5. Mn represents a number average molecular weight.

In the component (A ′), as the resin (A1), one type may be used alone, or two or more types may be used in combination.
When two or more kinds of the resin (A1) are used in combination, the lithography characteristics such as line width roughness (LWR), tilt margin, MEF, depth of focus (DOF), etc. are improved. It is preferable to use together resin (A1-15) represented by 15) and resin (A1-16) represented by the above formula (A1-16).
The mixing ratio (mass ratio) of the resin (A1-15) and the resin (A1-16) is not particularly limited, and considering the above effects, the resin (A1-15): resin (A1-16) ) = 9: 1 to 1: 9, preferably 8: 2 to 2: 8, and most preferably 7: 3 to 3: 7. Within the above range, the lithography properties are further improved.

In addition to the resin (A1), other polymer compounds known for use in positive resist compositions, such as hydroxystyrene resin, novolac resin, acrylic resin, etc., can also be contained in the component (A). It is.
However, the proportion of the resin (A1) in the component (A ′) is preferably 50% by mass or more, more preferably 70% by mass or more, and particularly preferably 80% by mass or more. Most preferably, it is 100 mass%.

Resin (A1) is a monomer derived from each structural unit, for example, a radical polymerization initiator such as azobisisobutyronitrile (AIBN), dimethyl-2,2′-azobis (2-methylpropionate). It can obtain by making it superpose | polymerize by the well-known radical polymerization etc. which were used.
In addition, the resin (A1) is used in combination with a chain transfer agent such as HS—CH ₂ —CH ₂ —CH ₂ —C (CF ₃ ) ₂ —OH at the time of the above-described polymerization. A —C (CF ₃ ) ₂ —OH group may be introduced into the. As described above, a resin having a hydroxyalkyl group in which a part of hydrogen atoms of an alkyl group is substituted with a fluorine atom reduces development defects and LER (line edge roughness: uneven unevenness of line side walls). It is effective for.
Moreover, (A ') component can be obtained by mixing each resin obtained by the said method, for example.

The mass average molecular weight (Mw) of the component (A ′) (polystyrene conversion standard by gel permeation chromatography) is not particularly limited, but is preferably 2000 to 50000, more preferably 3000 to 30000, and 5000 to 20000. Most preferred. If it is smaller than the upper limit of this range, there is sufficient solubility in a resist solvent to be used as a resist, and if it is larger than the lower limit of this range, dry etching resistance and resist pattern cross-sectional shape are good.
Further, the dispersity (Mw / Mn) of the component (A ′) is preferably 1.0 to 5.0, more preferably 1.0 to 3.0, and most preferably 1.2 to 2.5.
In the positive resist composition of the present invention, the content of the component (A ′) may be appropriately adjusted according to the resist film thickness to be formed.

<(B) component>
The component (B) is not particularly limited, and those that have been proposed as acid generators for chemically amplified resists can be used. Examples of such acid generators include onium salt acid generators such as iodonium salts and sulfonium salts, oxime sulfonate acid generators, bisalkyl or bisarylsulfonyldiazomethanes, poly (bissulfonyl) diazomethanes, and the like. There are various known diazomethane acid generators, nitrobenzyl sulfonate acid generators, imino sulfonate acid generators, disulfone acid generators, and the like.

  As the onium salt acid generator, for example, an acid generator represented by the following general formula (b-0) can be preferably used.

[Wherein, R ⁵¹ represents a linear, branched or cyclic alkyl group, or a linear, branched or cyclic fluorinated alkyl group; R ⁵² represents a hydrogen atom, a hydroxyl group, a halogen atom, linear or A branched alkyl group, a linear or branched halogenated alkyl group, or a linear or branched alkoxy group; R ⁵³ is an aryl group which may have a substituent; u '' Is an integer of 1 to 3. ]

In the general formula (b-0), R ⁵¹ represents a linear, branched or cyclic alkyl group, or a linear, branched or cyclic fluorinated alkyl group.
The linear or branched alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and most preferably 1 to 4 carbon atoms.
The cyclic alkyl group preferably has 4 to 12 carbon atoms, more preferably 5 to 10 carbon atoms, and most preferably 6 to 10 carbon atoms.
The fluorinated alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and most preferably 1 to 4 carbon atoms.
Further, the fluorination rate of the fluorinated alkyl group (ratio of the number of substituted fluorine atoms to the total number of hydrogen atoms in the alkyl group) is preferably 10 to 100%, more preferably 50 to 100%. Those in which all hydrogen atoms are substituted with fluorine atoms are preferred because the strength of the acid is increased.
R ⁵¹ is most preferably a linear alkyl group or a fluorinated alkyl group.

R ⁵² is a hydrogen atom, a hydroxyl group, a halogen atom, a linear or branched alkyl group, a linear or branched alkyl halide group, or a linear or branched alkoxy group.
In R ⁵² , examples of the halogen atom include a fluorine atom, a bromine atom, a chlorine atom, and an iodine atom, and a fluorine atom is preferable.
In R ⁵² , the alkyl group is linear or branched, and the carbon number thereof is preferably 1 to 5, particularly 1 to 4, and more preferably 1 to 3.
In R ⁵² , the halogenated alkyl group is a group in which part or all of the hydrogen atoms in the alkyl group are substituted with halogen atoms. Examples of the alkyl group herein are the same as the “alkyl group” in R ⁵² . Examples of the halogen atom to be substituted include the same as those described above for the “halogen atom”. In the halogenated alkyl group, it is desirable that 50 to 100% of the total number of hydrogen atoms are substituted with halogen atoms, and it is more preferable that all are substituted.
In R ⁵² , the alkoxy group is linear or branched, and the carbon number thereof is preferably 1 to 5, particularly 1 to 4, and more preferably 1 to 3.
Among these, R ⁵² is preferably a hydrogen atom.

R ⁵³ is an aryl group which may have a substituent, and examples of the structure of the basic ring (matrix ring) excluding the substituent include a naphthyl group, a phenyl group, an anthracenyl group, and the like. From the viewpoint of absorption of exposure light such as ArF excimer laser, a phenyl group is desirable.
Examples of the substituent include a hydroxyl group and a lower alkyl group (straight or branched chain, preferably having 5 or less carbon atoms, particularly preferably a methyl group).
As the aryl group for R ^53, an aryl group having no substituent is more preferable.
u ″ is an integer of 1 to 3, preferably 2 or 3, and particularly preferably 3.

  Preferable examples of the acid generator represented by the general formula (b-0) include the following.

  The acid generator represented by general formula (b-0) can be used alone or in combination of two or more.

  In addition, as another onium salt-based acid generator represented by the general formula (b-0), for example, a compound represented by the following general formula (b-1) or (b-2) is also preferable. Used.

［式中、Ｒ^１”〜Ｒ^３”，Ｒ^５”〜Ｒ^６”は、それぞれ独立に、アリール基またはアルキル基を表し；Ｒ^４”は、直鎖、分岐または環状のアルキル基またはフッ素化アルキル基を表し；Ｒ^１”〜Ｒ^３”のうち少なくとも１つはアリール基を表し、Ｒ^５”〜Ｒ^６”のうち少なくとも１つはアリール基を表す。］

[Wherein R ¹ ″ to R ³ ″ and R ⁵ ″ to R ⁶ ″ each independently represents an aryl group or an alkyl group; R ⁴ ″ represents a linear, branched or cyclic alkyl group or fluorinated group. Represents an alkyl group; at least one of R ¹ ″ to R ³ ″ represents an aryl group, and at least one of R ⁵ ″ to R ⁶ ″ represents an aryl group.]

In formula (b-1), R ¹ ″ to R ³ ″ each independently represents an aryl group or an alkyl group. At least one of R ¹ ″ to R ³ ″ represents an aryl group. Of R ¹ ″ to R ³ ″, two or more are preferably aryl groups, and most preferably all R ¹ ″ to R ³ ″ are aryl groups.
The aryl group for R ¹ ″ to R ³ ″ is not particularly limited and is, for example, an aryl group having 6 to 20 carbon atoms, in which part or all of the hydrogen atoms are alkyl groups, alkoxy groups It may or may not be substituted with a group, a halogen atom or the like. The aryl group is preferably an aryl group having 6 to 10 carbon atoms because it can be synthesized at a low cost. Specific examples include a phenyl group and a naphthyl group.
The alkyl group that may be substituted for the hydrogen atom of the aryl group is preferably an alkyl group having 1 to 5 carbon atoms, and is a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group. Is most preferred.
The alkoxy group that may be substituted for the hydrogen atom of the aryl group is preferably an alkoxy group having 1 to 5 carbon atoms, and most preferably a methoxy group or an ethoxy group.
The halogen atom that may be substituted for the hydrogen atom of the aryl group is preferably a fluorine atom.
The alkyl group for R 1 ^{"~R 3",} is not particularly limited, for example, a straight, include alkyl groups such as branched or cyclic. It is preferable that it is C1-C5 from the point which is excellent in resolution. Specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an n-pentyl group, a cyclopentyl group, a hexyl group, a cyclohexyl group, a nonyl group, and a decanyl group. A methyl group is preferable because it is excellent in resolution and can be synthesized at low cost.
Among these, R ¹ ″ to R ³ ″ are most preferably a phenyl group or a naphthyl group, respectively.

R ⁴ ″ represents a linear, branched or cyclic alkyl group or a fluorinated alkyl group.
The linear or branched alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and most preferably 1 to 4 carbon atoms.
The cyclic alkyl group is a cyclic group as indicated by R ¹ ″ and preferably has 4 to 15 carbon atoms, more preferably 4 to 10 carbon atoms, and more preferably 6 carbon atoms. Most preferably, it is -10.
The fluorinated alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and most preferably 1 to 4 carbon atoms.
The fluorination rate of the fluorinated alkyl group (ratio of fluorine atoms in the alkyl group) is preferably 10 to 100%, more preferably 50 to 100%. Particularly, all the hydrogen atoms are substituted with fluorine atoms. It is preferable because the strength of the acid is increased.
R ⁴ ″ is most preferably a linear or cyclic alkyl group or a fluorinated alkyl group.

In formula (b-2), R ⁵ ″ to R ⁶ ″ each independently represents an aryl group or an alkyl group. At least one of R ⁵ ″ to R ⁶ ″ represents an aryl group. Of R ⁵ ″ to R ⁶ ″, two or more are preferably aryl groups, and most preferably R ⁵ ″ to R ⁶ ″ are all aryl groups.
As the aryl group for R ⁵ ″ to R ⁶ ″, the same as the aryl groups for R ¹ ″ to R ³ ″ can be used.
Examples of the alkyl group for R ⁵ ″ to R ⁶ ″ include the same as the alkyl group for R ¹ ″ to R ³ ″.
Among these, it is most preferable that all of R ⁵ ″ to R ⁶ ″ are phenyl groups.
"The, ^{R 4} in the formula (b-1)" ^{R 4} in the In the formula (b-2) include the same as.

  Specific examples of the onium salt acid generators represented by formulas (b-1) and (b-2) include diphenyliodonium trifluoromethanesulfonate or nonafluorobutanesulfonate, bis (4-tert-butylphenyl) iodonium. Trifluoromethane sulfonate or nonafluorobutane sulfonate, triphenylsulfonium trifluoromethane sulfonate, its heptafluoropropane sulfonate or its nonafluorobutane sulfonate, tri (4-methylphenyl) sulfonium trifluoromethane sulfonate, its heptafluoropropane sulfonate or its Nonafluorobutanesulfonate, dimethyl (4-hydroxynaphthyl) sulfonium trifluoromethanesulfonate, its heptaful Lopropanesulfonate or its nonafluorobutanesulfonate, trifluoromethanesulfonate of monophenyldimethylsulfonium, its heptafluoropropanesulfonate or its nonafluorobutanesulfonate, trifluoromethanesulfonate of diphenylmonomethylsulfonium, its heptafluoropropanesulfonate or its nonafluorobutanesulfonate (4-methylphenyl) diphenylsulfonium trifluoromethanesulfonate, its heptafluoropropane sulfonate or its nonafluorobutane sulfonate, (4-methoxyphenyl) diphenylsulfonium trifluoromethanesulfonate, its heptafluoropropane sulfonate or its nonafluorobutane sulfonate , Trifluoromethanesulfonate of tri (4-tert-butyl) phenylsulfonium, its heptafluoropropanesulfonate or its nonafluorobutanesulfonate, trifluoromethanesulfonate of diphenyl (1- (4-methoxy) naphthyl) sulfonium, its heptafluoropropane Sulfonate or its nonafluorobutane sulfonate, di (1-naphthyl) phenylsulfonium trifluoromethane sulfonate, its heptafluoropropane sulfonate or its nonafluorobutane sulfonate. In addition, onium salts in which the anion portion of these onium salts is replaced with methanesulfonate, n-propanesulfonate, n-butanesulfonate, or n-octanesulfonate can also be used.

  In addition, in the general formula (b-1) or (b-2), an onium salt-based acid generator in which the anion moiety is replaced with an anion moiety represented by the following general formula (b-3) or (b-4). Can also be used (the cation moiety is the same as (b-1) or (b-2)).

［式中、Ｘ”は、少なくとも１つの水素原子がフッ素原子で置換された炭素数２〜６のアルキレン基を表し；Ｙ”、Ｚ”は、それぞれ独立に、少なくとも１つの水素原子がフッ素原子で置換された炭素数１〜１０のアルキル基を表す。］

[Wherein X ″ represents an alkylene group having 2 to 6 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom; Y ″ and Z ″ each independently represent at least one hydrogen atom as a fluorine atom; Represents an alkyl group having 1 to 10 carbon atoms and substituted with

X ″ is a linear or branched alkylene group in which at least one hydrogen atom is substituted with a fluorine atom, and the alkylene group has 2 to 6 carbon atoms, preferably 3 to 5 carbon atoms, Preferably it is C3.
Y ″ and Z ″ are each independently a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and the alkyl group has 1 to 10 carbon atoms, preferably It is C1-C7, More preferably, it is C1-C3.
The carbon number of the alkylene group of X ″ or the carbon number of the alkyl group of Y ″ and Z ″ is preferably as small as possible because the solubility in the resist solvent is good within the above carbon number range.
In addition, in the alkylene group of X ″ or the alkyl group of Y ″ and Z ″, as the number of hydrogen atoms substituted with fluorine atoms increases, the strength of the acid increases, and high-energy light or electron beam of 200 nm or less The ratio of fluorine atoms in the alkylene group or alkyl group, that is, the fluorination rate is preferably 70 to 100%, more preferably 90 to 100%, and most preferably all. Are a perfluoroalkylene group or a perfluoroalkyl group in which a hydrogen atom is substituted with a fluorine atom.

  In this specification, the oxime sulfonate acid generator is a compound having at least one group represented by the following general formula (B-1), and has a property of generating an acid upon irradiation with radiation. is there. Such oxime sulfonate-based acid generators are frequently used for chemically amplified resist compositions, and can be arbitrarily selected and used.

（式（Ｂ−１）中、Ｒ^３１、Ｒ^３２はそれぞれ独立に有機基を表す。）

(In formula (B-1), R ³¹ and R ³² each independently represents an organic group.)

The organic groups of R ³¹ and R ³² are groups containing carbon atoms, and atoms other than carbon atoms (for example, hydrogen atoms, oxygen atoms, nitrogen atoms, sulfur atoms, halogen atoms (fluorine atoms, chlorine atoms, etc.), etc.) You may have.
As the organic group for R ³¹ , a linear, branched, or cyclic alkyl group or aryl group is preferable. These alkyl groups and aryl groups may have a substituent. There is no restriction | limiting in particular as this substituent, For example, a fluorine atom, a C1-C6 linear, branched or cyclic alkyl group etc. are mentioned. Here, “having a substituent” means that part or all of the hydrogen atoms of the alkyl group or aryl group are substituted with a substituent.
As an alkyl group, C1-C20 is preferable, C1-C10 is more preferable, C1-C8 is more preferable, C1-C6 is especially preferable, and C1-C4 is the most preferable. As the alkyl group, a partially or completely halogenated alkyl group (hereinafter sometimes referred to as a halogenated alkyl group) is particularly preferable. The partially halogenated alkyl group means an alkyl group in which a part of hydrogen atoms is substituted with a halogen atom, and the fully halogenated alkyl group means that all of the hydrogen atoms are halogen atoms. Means an alkyl group substituted with Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is particularly preferable. That is, the halogenated alkyl group is preferably a fluorinated alkyl group.
The aryl group preferably has 4 to 20 carbon atoms, more preferably 4 to 10 carbon atoms, and most preferably 6 to 10 carbon atoms. As the aryl group, a partially or completely halogenated aryl group is particularly preferable. The partially halogenated aryl group means an aryl group in which a part of hydrogen atoms is substituted with a halogen atom, and the fully halogenated aryl group means that all of the hydrogen atoms are halogen atoms. Means an aryl group substituted with.
R ³¹ is particularly preferably an alkyl group having 1 to 4 carbon atoms having no substituent or a fluorinated alkyl group having 1 to 4 carbon atoms.

As the organic group for R ³² , a linear, branched, or cyclic alkyl group, aryl group, or cyano group is preferable. As the alkyl group and aryl group for R ^32, the same alkyl groups and aryl groups as those described above for R ³¹ can be used.
R ³² is particularly preferably a cyano group, an alkyl group having 1 to 8 carbon atoms having no substituent, or a fluorinated alkyl group having 1 to 8 carbon atoms.

  More preferable examples of the oxime sulfonate-based acid generator include compounds represented by the following general formula (B-2) or (B-3).

［式（Ｂ−２）中、Ｒ^３３は、シアノ基、置換基を有さないアルキル基またはハロゲン化アルキル基である。Ｒ^３４はアリール基である。Ｒ^３５は置換基を有さないアルキル基またはハロゲン化アルキル基である。］

[In Formula (B-2), R ³³ represents a cyano group, an alkyl group having no substituent, or a halogenated alkyl group. R ³⁴ is an aryl group. R ³⁵ represents an alkyl group having no substituent or a halogenated alkyl group. ]

［式（Ｂ−３）中、Ｒ^３６はシアノ基、置換基を有さないアルキル基またはハロゲン化アルキル基である。Ｒ^３７は２または３価の芳香族炭化水素基である。Ｒ^３８は置換基を有さないアルキル基またはハロゲン化アルキル基である。ｐ’’は２または３である。］

[In Formula (B-3), R ³⁶ represents a cyano group, an alkyl group having no substituent, or a halogenated alkyl group. R ³⁷ is a divalent or trivalent aromatic hydrocarbon group. ^R38 is an alkyl group having no substituent or a halogenated alkyl group. p ″ is 2 or 3. ]

In the general formula (B-2), the alkyl group or halogenated alkyl group having no substituent for R ³³ preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and more preferably carbon atoms. Numbers 1 to 6 are most preferable.
R ³³ is preferably a halogenated alkyl group, more preferably a fluorinated alkyl group.
The fluorinated alkyl group for R ³³ is preferably such that the hydrogen atom of the alkyl group is 50% or more fluorinated, more preferably 70% or more, and still more preferably 90% or more.

As the aryl group of R ³⁴ , one hydrogen atom is removed from an aromatic hydrocarbon ring such as a phenyl group, a biphenyl group, a fluorenyl group, a naphthyl group, an anthracyl group, or a phenanthryl group. And heteroaryl groups in which some of the carbon atoms constituting the ring of these groups are substituted with heteroatoms such as oxygen, sulfur, and nitrogen atoms. Among these, a fluorenyl group is preferable.
The aryl group of R ³⁴ may have a substituent such as an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group, or an alkoxy group. The alkyl group or halogenated alkyl group in the substituent preferably has 1 to 8 carbon atoms, and more preferably 1 to 4 carbon atoms. The halogenated alkyl group is preferably a fluorinated alkyl group.

The alkyl group or halogenated alkyl group having no substituent for R ³⁵ preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and most preferably 1 to 6 carbon atoms.
R ³⁵ is preferably a halogenated alkyl group, more preferably a fluorinated alkyl group, and most preferably a partially fluorinated alkyl group.
The fluorinated alkyl group in R ³⁵ preferably has 50% or more of the hydrogen atom of the alkyl group fluorinated, more preferably 70% or more, and even more preferably 90% or more. This is preferable because the strength of the acid is increased. Most preferably, it is a fully fluorinated alkyl group in which a hydrogen atom is 100% fluorine-substituted.

In the general formula (B-3), the alkyl group or halogenated alkyl group having no substituent for R ³⁶ is the same as the alkyl group or halogenated alkyl group having no substituent for R ^33. Is mentioned.
Examples of the divalent or trivalent aromatic hydrocarbon group for R ³⁷ include groups obtained by further removing one or two hydrogen atoms from the aryl group for R ³⁴ .
Examples of the alkyl group or halogenated alkyl group having no substituent of R ³⁸ include the same alkyl groups or halogenated alkyl groups as those having no substituent of R ³⁵ .
p ″ is preferably 2.

Specific examples of the oxime sulfonate acid generator include α- (p-toluenesulfonyloxyimino) -benzyl cyanide, α- (p-chlorobenzenesulfonyloxyimino) -benzyl cyanide, α- (4-nitrobenzenesulfonyloxy). Imino) -benzylcyanide, α- (4-nitro-2-trifluoromethylbenzenesulfonyloxyimino) -benzylcyanide, α- (benzenesulfonyloxyimino) -4-chlorobenzylcyanide, α- (benzenesulfonyl) Oxyimino) -2,4-dichlorobenzyl cyanide, α- (benzenesulfonyloxyimino) -2,6-dichlorobenzyl cyanide, α- (benzenesulfonyloxyimino) -4-methoxybenzyl cyanide, α- ( 2-Chlorobenzenesulfonyloxyimino) 4-methoxybenzylcyanide, α- (benzenesulfonyloxyimino) -thien-2-ylacetonitrile, α- (4-dodecylbenzenesulfonyloxyimino) -benzylcyanide, α-[(p-toluenesulfonyloxyimino) -4-methoxyphenyl] acetonitrile, α-[(dodecylbenzenesulfonyloxyimino) -4-methoxyphenyl] acetonitrile, α- (tosyloxyimino) -4-thienyl cyanide, α- (methylsulfonyloxyimino) -1-cyclo Pentenyl acetonitrile, α- (methylsulfonyloxyimino) -1-cyclohexenylacetonitrile, α- (methylsulfonyloxyimino) -1-cycloheptenylacetonitrile, α- (methylsulfonyloxyimino) -1-cyclooctene Acetonitrile, α- (trifluoromethylsulfonyloxyimino) -1-cyclopentenylacetonitrile, α- (trifluoromethylsulfonyloxyimino) -cyclohexylacetonitrile, α- (ethylsulfonyloxyimino) -ethylacetonitrile, α- (propyl Sulfonyloxyimino) -propylacetonitrile, α- (cyclohexylsulfonyloxyimino) -cyclopentylacetonitrile, α- (cyclohexylsulfonyloxyimino) -cyclohexylacetonitrile, α- (cyclohexylsulfonyloxyimino) -1-cyclopentenylacetonitrile, α- ( Ethylsulfonyloxyimino) -1-cyclopentenylacetonitrile, α- (isopropylsulfonyloxyimino) -1-cyclope N-tenyl acetonitrile, α- (n-butylsulfonyloxyimino) -1-cyclopentenylacetonitrile, α- (ethylsulfonyloxyimino) -1-cyclohexenylacetonitrile, α- (isopropylsulfonyloxyimino) -1-cyclohexenylacetonitrile , Α- (n-butylsulfonyloxyimino) -1-cyclohexenylacetonitrile, α- (methylsulfonyloxyimino) -phenylacetonitrile, α- (methylsulfonyloxyimino) -p-methoxyphenylacetonitrile, α- (trifluoro Methylsulfonyloxyimino) -phenylacetonitrile, α- (trifluoromethylsulfonyloxyimino) -p-methoxyphenylacetonitrile, α- (ethylsulfonyloxyimino) -p- Butoxy phenylacetonitrile, alpha-(propylsulfonyl oxyimino)-p-methylphenyl acetonitrile, alpha-like (methylsulfonyloxyimino)-p-bromophenyl acetonitrile.
Further, an oxime sulfonate-based acid generator disclosed in JP-A-9-208554 (paragraphs [0012] to [0014] [chemical formula 18] to [chemical formula 19]), pamphlet of International Publication No. 04/074242, An oxime sulfonate-based acid generator disclosed in Examples 1 to 40) on pages 65 to 85 can also be suitably used.
Moreover, the following can be illustrated as a suitable thing.

  Of the above exemplified compounds, the following four compounds are preferred.

Among diazomethane acid generators, specific examples of bisalkyl or bisarylsulfonyldiazomethanes include bis (isopropylsulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, Examples include bis (cyclohexylsulfonyl) diazomethane, bis (2,4-dimethylphenylsulfonyl) diazomethane, and the like.
Further, diazomethane acid generators disclosed in JP-A-11-035551, JP-A-11-035552, and JP-A-11-035573 can also be suitably used.
Examples of poly (bissulfonyl) diazomethanes include 1,3-bis (phenylsulfonyldiazomethylsulfonyl) propane and 1,4-bis (phenylsulfonyldiazo) disclosed in JP-A-11-322707. Methylsulfonyl) butane, 1,6-bis (phenylsulfonyldiazomethylsulfonyl) hexane, 1,10-bis (phenylsulfonyldiazomethylsulfonyl) decane, 1,2-bis (cyclohexylsulfonyldiazomethylsulfonyl) ethane, 1,3 -Bis (cyclohexylsulfonyldiazomethylsulfonyl) propane, 1,6-bis (cyclohexylsulfonyldiazomethylsulfonyl) hexane, 1,10-bis (cyclohexylsulfonyldiazomethylsulfonyl) decane, etc. Door can be.

(B) As a component, these acid generators may be used individually by 1 type, and may be used in combination of 2 or more type.
In the present invention, it is particularly preferable to use an onium salt having a fluorinated alkyl sulfonate ion as an anion as the component (B). Specific examples include triphenylsulfonium nonafluorobutane sulfonate. In addition, di (1-naphthyl) phenylsulfonium nonafluorobutanesulfonate, (4-methylphenyl) diphenylsulfonium nonafluorobutanesulfonate, and the like are also included.
Content of (B) component in the positive resist composition of this invention is 0.5-30 mass parts with respect to 100 mass parts of (A) component, Preferably it is 1-15 mass parts. By setting it within the above range, pattern formation is sufficiently performed. Moreover, since a uniform solution is obtained and storage stability becomes favorable, it is preferable.

<(D) component>
In the positive resist composition of the present invention, a nitrogen-containing organic compound (D) (hereinafter referred to as “component (D)”) is further added as an optional component in order to improve the resist pattern shape, stability over time and the like. It is preferable to contain.
Since a wide variety of components (D) have already been proposed, any known one may be used. Cyclic amines, aliphatic amines, particularly secondary aliphatic amines and tertiary fats may be used. Group amines are preferred.
Examples of the aliphatic amine include amines (alkyl amines or alkyl alcohol amines) in which at least one hydrogen atom of ammonia NH ₃ is substituted with an alkyl group or hydroxyalkyl group having 12 or less carbon atoms. Specific examples thereof include monoalkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine; diethylamine, di-n-propylamine, di-n-heptylamine, Dialkylamines such as di-n-octylamine and dicyclohexylamine; trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-hexylamine, tri-n-pentylamine, tri-n-heptyl Trialkylamines such as amine, tri-n-octylamine, tri-n-nonylamine, tri-n-decanylamine, tri-n-dodecylamine; diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, di-n -Ok Noruamin, alkyl alcohol amines such as tri -n- octanol amine.
Among these, alkyl alcohol amines and trialkyl amines are preferable, and alkyl alcohol amines are most preferable. Among the alkyl alcohol amines, triethanolamine and triisopropanolamine are preferable, and triethanolamine is most preferable. Of the trialkylamines, tri-n-octylamine is particularly preferable.
Examples of the cyclic amine include heterocyclic compounds containing a nitrogen atom as a hetero atom. The heterocyclic compound may be monocyclic (aliphatic monocyclic amine) or polycyclic (aliphatic polycyclic amine).
Specific examples of the aliphatic monocyclic amine include piperidine and piperazine.
As the aliphatic polycyclic amine, those having 6 to 10 carbon atoms are preferable. Specifically, 1,5-diazabicyclo [4.3.0] -5-nonene, 1,8-diazabicyclo [5. 4.0] -7-undecene, hexamethylenetetramine, 1,4-diazabicyclo [2.2.2] octane, and the like.
These may be used alone or in combination of two or more.
In the present invention, it is particularly preferable to use an alkyl alcohol amine as the component (D). Specifically, triethanolamine or the like. Moreover, it is also preferable to use an alkylamine, specifically, tri-n-octylamine or the like.
(D) component is normally used in 0.01-5.0 mass parts with respect to 100 mass parts of (A) component.

<Optional component>
In the positive resist composition of the present invention, an organic carboxylic acid or an oxo acid of phosphorus or a derivative thereof (E) is used as an optional component for the purpose of preventing sensitivity deterioration and improving the resist pattern shape, retention stability, and the like. ) (Hereinafter referred to as component (E)).
As the organic carboxylic acid, for example, acetic acid, 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 other phosphoric acid or derivatives thereof such as phosphonic acid, phosphonic acid dimethyl ester, phosphonic acid- Like phosphonic acids such as di-n-butyl ester, phenylphosphonic acid, phosphonic acid diphenyl ester, phosphonic acid dibenzyl ester and derivatives thereof, phosphinic acids such as phosphinic acid, phenylphosphinic acid and their esters Among these, phosphonic acid is particularly preferable.
(E) A component may be used individually by 1 type and may use 2 or more types together.
As the component (E), an organic carboxylic acid is preferable, and salicylic acid is particularly preferable.
(E) A component is used in the ratio of 0.01-5.0 mass parts per 100 mass parts of (A) component.

  The positive resist composition of the present invention further contains miscible additives as desired, for example, additional resins for improving the performance of the resist film, surfactants for improving coating properties, dissolution inhibitors, Plasticizers, stabilizers, colorants, antihalation agents, dyes, and the like can be added and contained as appropriate.

The positive resist composition of the present invention can be produced by dissolving the material in an organic solvent (hereinafter sometimes referred to as (S) component).
As the component (S), any component can be used as long as it can dissolve each component to be used to form a uniform solution. Conventionally, any one of known solvents for chemically amplified resists can be used. Two or more types can be appropriately selected and used.
For example, lactones such as γ-butyrolactone; ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl-n-amyl ketone, methyl isoamyl ketone, 2-heptanone; polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol And derivatives thereof; compounds having an ester bond such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, dipropylene glycol monoacetate, monomethyl ethers of the polyhydric alcohols or compounds having the ester bond, mono Monoalkyl ethers such as ethyl ether, monopropyl ether, monobutyl ether or monophenyl ether Derivatives of polyhydric alcohols such as compounds having an ether bond; cyclic ethers such as dioxane, methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, Esters such as methyl methoxypropionate and ethyl ethoxypropionate; anisole, ethylbenzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenetol, butylphenyl ether, ethylbenzene, diethylbenzene, amylbenzene, isopropylbenzene, toluene, xylene And aromatic organic solvents such as cymene and mesitylene.
These organic solvents may be used independently and may be used as 2 or more types of mixed solvents.
Among these, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), and EL are preferable.
Moreover, the mixed solvent which mixed PGMEA and the polar solvent is preferable. The blending ratio (mass ratio) may be appropriately determined in consideration of the compatibility between PGMEA and the polar solvent, preferably 1: 9 to 9: 1, more preferably 2: 8 to 8: 2. It is preferable to be within the range.
More specifically, when EL is blended as a polar solvent, the mass ratio of PGMEA: EL is preferably 1: 9 to 9: 1, more preferably 2: 8 to 8: 2. Moreover, when mix | blending PGME as a polar solvent, the mass ratio of PGMEA: PGME becomes like this. Preferably it is 1: 9-9: 1, More preferably, it is 2: 8-8: 2, More preferably, it is 3: 7-7: 3.
In addition, as the component (S), a mixed solvent of at least one selected from PGMEA and EL and γ-butyrolactone is also preferable. In this case, the mixing ratio of the former and the latter is preferably 70:30 to 95: 5.
The amount of the component (S) used is not particularly limited, but is a concentration that can be applied to a substrate or the like, and is appropriately set according to the coating film thickness. -20% by mass, preferably 5-15% by mass.

(Negative resist composition)
The negative resist composition in the present invention contains the component (A ″), the component (B), and the component (C).
Such a negative resist composition is alkali-soluble before exposure. When an acid is generated from the component (B) by exposure, the acid acts to cause crosslinking between the component (A ″) and the component (C). Therefore, when the resist film formed by applying the negative resist composition on the substrate is selectively exposed in the formation of the resist pattern, the exposed portion becomes alkali-insoluble, but not yet exposed. The exposed portion remains alkali-soluble, and a negative resist pattern can be formed by alkali development.

<(A ") component>
In such a negative resist composition, the component (A ″) includes a resin (A1) having a structural unit (a0) represented by the general formula (a-0).
Preferably, the resin (A1) is composed of the structural unit (a0).

・ Structural unit (a0)
The resin (A1) includes a structural unit (a0) represented by the general formula (a-0). A negative resist composition using the resin (A1) can form a resist pattern.
In the general formula (a-0), the substitution positions of R, a, b, c, and the hydroxyl group are all the same as in the case of the positive resist composition.
Further, the preferred structural unit as the structural unit (a0) is the same as that of the positive resist composition.

In the resin (A1) contained in the negative resist composition, as the structural unit (a0), one type of structural unit may be used alone, or two or more types may be used in combination.
The proportion of the structural unit (a0) in the resin (A1) is preferably 50 mol% or more, more preferably 70 mol% or more, and more preferably 100 mol% with respect to the total of all the structural units constituting the resin (A1). It may be. Most preferably, it is 100 mol%, and the resin (A1) is most preferably a polymer composed of the structural unit (a0). By setting it to be equal to or higher than the lower limit of the range, the effect of including the structural unit (a0) can be sufficiently obtained.

The resin (A1) contained in the negative resist composition of the present invention may have a structural unit other than the structural unit (a0).
As such a constitutional unit, a constitutional unit used in a known resin component for conventional chemically amplified resist compositions can be used, for example, a constitution containing an aliphatic cyclic group having a fluorinated hydroxyalkyl group. A structural unit derived from an acrylic ester containing a unit, a hydroxyl group-containing aliphatic cyclic group, a structural unit derived from acrylic acid having no cyclic structure and having an alcoholic hydroxyl group in the side chain, etc. Can be mentioned.

The resin (A1) contained in the negative resist composition has a mass average molecular weight (Mw; polystyrene-reduced mass average molecular weight by gel permeation chromatography) of preferably 2000 to 30000, more preferably 2000 to 10,000, and still more preferably 3000. ~ 8000. By setting it within this range, a good dissolution rate in an alkaline developer can be obtained, which is preferable from the viewpoint of high resolution. When the mass average molecular weight is lower within this range, good characteristics tend to be obtained.
Further, the dispersity (Mw / number average molecular weight (Mn)) is preferably 1.0 to 5.0, and more preferably 1.0 to 2.5.

  The resin (A1) can be obtained, for example, by radical polymerization of a monomer for deriving each structural unit by a conventional method.

In the component (A ″), one or more of the resins (A1) can be mixed and used.
In addition to the resin (A1), other polymer compounds known for negative resist compositions, such as hydroxystyrene resin, novolak resin, acrylic resin, etc., can also be contained in the component (A). It is.
However, the proportion of the resin (A1) in the component (A ″) is preferably 50% by mass or more, more preferably 70% by mass or more, and particularly preferably 80% by mass or more. Most preferably, it is 100 mass%.

<(B) component>
The component (B) is the same as that of the positive resist composition.
In the negative resist composition of the present invention, it is particularly preferable to use an onium salt having a fluorinated alkyl sulfonate ion as an anion as the component (B). Specific examples include triphenylsulfonium trifluoromethanesulfonate.
Content of (B) component in the negative resist composition in this invention is 0.5-30 mass parts with respect to 100 mass parts of (A) component, Preferably it is 1-15 mass parts. By setting it within the above range, pattern formation is sufficiently performed. Moreover, since a uniform solution is obtained and storage stability becomes favorable, it is preferable.

<(C) component>
The component (C) is not particularly limited, and can be arbitrarily selected from cross-linking agents used in chemically amplified negative resist compositions known so far.
Specifically, for example, 2,3-dihydroxy-5-hydroxymethylnorbornane, 2-hydroxy-5,6-bis (hydroxymethyl) norbornane, cyclohexanedimethanol, 3,4,8 (or 9) -trihydroxytri Aliphatic cyclic carbonization having a hydroxyl group or a hydroxyalkyl group or both such as cyclodecane, 2-methyl-2-adamantanol, 1,4-dioxane-2,3-diol, 1,3,5-trihydroxycyclohexane Examples thereof include hydrogen and oxygen-containing derivatives thereof.

In addition, amino group-containing compounds such as melamine, acetoguanamine, benzoguanamine, urea, ethylene urea, propylene urea, glycoluril are reacted with formaldehyde or formaldehyde and lower alcohol, and the hydrogen atom of the amino group is hydroxymethyl group or lower alkoxymethyl. And a compound substituted with a group.
Of these, those using melamine are melamine-based crosslinking agents, those using urea are urea-based crosslinking agents, those using alkylene ureas such as ethylene urea and propylene urea are alkylene urea-based crosslinking agents, and glycoluril is used. This was called a glycoluril-based crosslinking agent.
The component (C) is preferably at least one selected from the group consisting of melamine-based crosslinking agents, urea-based crosslinking agents, alkylene urea-based crosslinking agents, and glycoluril-based crosslinking agents, and glycoluril-based crosslinking agents are particularly preferred. preferable.

  Melamine-based crosslinking agents include compounds in which melamine and formaldehyde are reacted to replace the amino group hydrogen atom with a hydroxymethyl group, and melamine, formaldehyde and lower alcohol are reacted to convert the amino group hydrogen atom into a lower alkoxy group. Examples include compounds substituted with a methyl group. Specific examples include hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, hexabutoxybutyl melamine, and the like, among which hexamethoxymethyl melamine is preferable.

  Urea-based crosslinking agents include compounds in which urea and formaldehyde are reacted to replace amino group hydrogen atoms with hydroxymethyl groups, and urea, formaldehyde and lower alcohols are reacted to convert amino group hydrogen atoms into lower alkoxy groups. Examples include compounds substituted with a methyl group. Specific examples include bismethoxymethylurea, bisethoxymethylurea, bispropoxymethylurea, bisbutoxymethylurea, etc. Among them, bismethoxymethylurea is preferable.

  As an alkylene urea type crosslinking agent, the compound represented by the following general formula (C-1) is mentioned.

（式中、Ｒ^５’とＲ^６’はそれぞれ独立に水酸基又は低級アルコキシ基であり、Ｒ^３’とＲ^４’はそれぞれ独立に水素原子、水酸基又は低級アルコキシ基であり、ｖは０又は１〜２の整数である。）

(Wherein R ⁵ ′ and R ⁶ ′ are each independently a hydroxyl group or a lower alkoxy group, R ³ ′ and R ⁴ ′ are each independently a hydrogen atom, a hydroxyl group or a lower alkoxy group, and v is 0 or 1 It is an integer of ~ 2.)

When R ⁵ ′ and R ⁶ ′ are lower alkoxy groups, they are preferably alkoxy groups having 1 to 4 carbon atoms, and may be linear or branched. R ⁵ ′ and R ⁶ ′ may be the same or different from each other. More preferably, they are the same.
When R ³ ′ and R ⁴ ′ are lower alkoxy groups, they are preferably alkoxy groups having 1 to 4 carbon atoms, and may be linear or branched. R ³ ′ and R ⁴ ′ may be the same or different from each other. More preferably, they are the same.
v is 0 or an integer of 1 to 2, preferably 0 or 1.
As the alkylene urea crosslinking agent, a compound in which v is 0 (ethylene urea crosslinking agent) and / or a compound in which v is 1 (propylene urea crosslinking agent) are particularly preferable.

  The compound represented by the general formula (C-1) can be obtained by a condensation reaction of alkylene urea and formalin and by reacting this product with a lower alcohol.

  Specific examples of the alkylene urea crosslinking agent include, for example, mono and / or dihydroxymethylated ethylene urea, mono and / or dimethoxymethylated ethylene urea, mono and / or diethoxymethylated ethylene urea, mono and / or dipropoxy Ethylene urea-based crosslinking agents such as methylated ethylene urea, mono and / or dibutoxymethylated ethylene urea; mono and / or dihydroxymethylated propylene urea, mono and / or dimethoxymethylated propylene urea, mono and / or diethoxymethyl Propylene urea-based crosslinkers such as propylene urea, mono and / or dipropoxymethylated propylene urea, mono and / or dibutoxymethylated propylene urea; 1,3-di (methoxymethyl) 4,5-dihydroxy-2- Imidazolidinone, 1,3-di (Metoki Like, etc.) -4,5-dimethoxy-2-imidazolidinone.

Examples of the glycoluril-based crosslinking agent include glycoluril derivatives in which the N position is substituted with one or both of a hydroxyalkyl group and an alkoxyalkyl group having 1 to 4 carbon atoms. Such a glycoluril derivative can be obtained by a condensation reaction between glycoluril and formalin and by reacting this product with a lower alcohol.
Specific examples of the glycoluril-based crosslinking agent include, for example, mono, di, tri and / or tetrahydroxymethylated glycoluril, mono, di, tri and / or tetramethoxymethylated glycoluril, mono, di, tri and / or Examples include tetraethoxymethylated glycoluril, mono, di, tri and / or tetrapropoxymethylated glycoluril, mono, di, tri and / or tetrabutoxymethylated glycoluril.

As the component (C), one type may be used alone, or two or more types may be used in combination.
The content of the component (C) is preferably 3 to 30 parts by mass, more preferably 3 to 15 parts by mass, and most preferably 5 to 10 parts by mass with respect to 100 parts by mass of the component (A ″). If the content is less than or equal to the lower limit, crosslinking formation proceeds sufficiently and a good resist pattern is obtained, and if it is less than or equal to this upper limit, the storage stability of the resist coating solution is good and the sensitivity is high. Over time is suppressed.

<(D) component>
The negative resist composition according to the present invention further contains 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 over time, and the like. It is preferable to contain.
The component (D) is the same as that of the positive resist composition.
In the negative resist composition of the present invention, among them, alkyl alcohol amines are preferable, and triethanolamine and triisopropanolamine are most preferable.
The content of the component (D) in the negative resist composition in the present invention is usually in the range of 0.01 to 5.0 parts by mass with respect to 100 parts by mass of the component (A ″).

<Optional component>
In the negative resist composition of the present invention, as optional components, (E) component, (S) component similar to those described in the positive resist composition, and optionally miscible additives, for example, Addition resin for improving performance of resist film, surfactant for improving coating property, dissolution inhibitor, plasticizer, stabilizer, colorant, antihalation agent, dye, etc. are added and contained as appropriate. Can do.
As the component (S), propylene glycol monomethyl ether (PGME) is most preferable from the viewpoint of the solubility of the component (A ″).
The amount of the component (S) used is not particularly limited, but is a concentration that can be applied to a substrate or the like, and is appropriately set according to the coating film thickness. -20% by mass, preferably 5-15% by mass.

≪Resist pattern formation method≫
The resist pattern forming method of the present invention can be performed, for example, as follows.
That is, first, the resist composition is applied onto a substrate such as a silicon wafer with a spinner or the like, and prebaked (PAB) is applied for 40 to 120 seconds, preferably 60 to 90 seconds under a temperature condition of 80 to 150 ° C., For example, ArF excimer laser light is selectively exposed through a desired mask pattern using, for example, an ArF exposure apparatus, and then PEB (post-exposure heating) is preferably performed for 40 to 120 seconds under a temperature condition of 80 to 150 ° C. Is applied for 60-90 seconds. Subsequently, this is developed using an alkali developer, for example, an aqueous solution of 0.1 to 10% by mass of tetramethylammonium hydroxide. In this way, a resist pattern faithful to the mask pattern can be obtained.
In some cases, a post-baking step may be included after the alkali development, and an organic or inorganic antireflection film may be provided between the substrate and the coating layer of the resist composition.
The wavelength used for exposure is not particularly limited, and ArF excimer laser, KrF excimer laser, F ₂ excimer laser, EUV (extreme ultraviolet), VUV (vacuum ultraviolet), EB (electron beam), X-ray, soft X-ray Or the like. The resist composition according to the present invention is particularly effective for an ArF excimer laser.

≪Resin≫
The resin of the present invention has the structural unit (a0) represented by the general formula (a-0). Preferably, the structural unit (a0) is 3-methacryloyloxy-4-hydroxytetrahydrofuran.
Such a resin is suitable as a resist resin. This resin is the same as the resin (A1) and will not be described.

According to the present invention, a novel resist composition can be provided. The role of the structural unit (a0) represented by the general formula (a-0) is assumed as follows.
In the positive resist composition, the structural unit (a0) is considered to play a role of adjusting the alkali solubility of the component (A ′) in the exposed portion. Thereby, it is estimated that a fine resist pattern can be formed in a positive resist composition.
The structural unit (a0) has a monocyclic group containing a hydroxyl group and having an oxygen atom on the ring skeleton. Therefore, it is a structural unit having high polarity and is considered to have good affinity with the developer. Therefore, it is considered that the component (A ′) can be quickly dissolved in the developer by the exposed portion. Moreover, it is thought that (A ') component of an unexposed part improves board | substrate adhesiveness by the effect | action of the hydroxyl group in the said structural unit (a0).

In the negative resist composition, it is considered that the structural unit (a0) plays a role of adjusting the alkali insolubility of the component (A ″) of the exposed portion by crosslinking with the crosslinking agent component by containing a hydroxyl group. Thus, it is estimated that a fine resist pattern can be formed in the negative resist composition.
Further, the hydroxyl group in the structural unit (a0) is bonded to the monocyclic group, and it is considered that the influence of steric hindrance is small in terms of crosslinkability with the crosslinking agent component. Therefore, it is considered that the crosslinkability is high and the alkali insolubilization of the (A ″) component in the exposed area is good. The (A ″) component in the unexposed area is the same as the exposed area in the positive resist composition. For this reason, it is considered that it can be quickly dissolved in the developer. Therefore, lithography properties such as resolution are good.

In addition, according to the present invention, in a positive resist composition, a resist pattern having a good shape with reduced line width roughness (LWR) indicating, for example, non-uniform line width of the line pattern can be obtained. Preferably, the resist pattern shape is good in a thin resist film.
Further, according to the present invention, a good mask error factor (MEF) and an exposure amount margin can be obtained in a positive resist composition.
Note that the exposure amount margin indicates a change amount of the pattern size accompanying a change in the exposure amount, and indicates that the change amount of the pattern size accompanying the change in the exposure amount is smaller as the exposure amount margin is larger.
In addition, according to the present invention, the positive resist composition also has an effect that the lithography characteristics such as collapse margin and depth of focus (DOF) are good.
Note that “falling margin” indicates the difficulty of falling a resist pattern when a fine resist pattern is resolved.
“DOF” means a range of depth of focus where a resist pattern can be formed with a dimension within which a deviation from a target dimension is within a predetermined range when exposure is performed with the exposure focus shifted up and down at the same exposure amount, that is, a mask pattern. This is the range where a faithful resist pattern can be obtained, and the larger the DOF, the better.

  EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited by these examples.

[Synthesis example]
The monomer which provides the structural unit (a0) in the present invention used in the synthesis of the resin component (A) in the examples is shown below.

HOTHMA: A monomer represented by the following chemical formula (3-methacryloyloxy-4-hydroxytetrahydrofuran).

The method for synthesizing the monomer will be described below. In the synthesis example, gas chromatography (GC) was measured using a TG-1 (inner diameter 0.25 mm, column length 30 m, film thickness 0.25 μm) capillary column (carrier gas: helium) manufactured by GL Science, Gel permeation chromatography (GPC) was measured using two TSK-GEL G2000H _XL columns (inner diameter 7.8 mm, column length 300 mm) manufactured by Tosoh Corporation in series (mobile phase: THF; column temperature 40 ° C.).

Synthesis example 1
Into a reactor in which nitrogen was passed, 20.00 g (192 mmol) of cis-3,4-dihydroxytetrahydrofuran, 15.50 g of triethylamine (153 mmol, 0.797 equivalent to cis-3,4-dihydroxytetrahydrofuran), tetrahydrofuran ( (THF) (150 mL) was charged, and the system was cooled with salt-ice so that the temperature inside the system became −5 ° C.
Into this, 13.79 g (128 mmol, 0.666 equivalent to cis-3,4-dihydroxytetrahydrofuran) of methacrylic acid chloride (purity 97% by mass) was slowly added dropwise over 60 minutes. After the dropping, the reaction was continued for 1 hour while slowly raising the temperature to 20 ° C. After completion of the reaction, the reaction solution was poured into 20 mL of saturated aqueous sodium hydrogen carbonate, and THF was distilled off with a rotary evaporator. The remaining aqueous layer was extracted 3 times with 50 mL of ethyl acetate. The ethyl acetate layer was washed once with 20 mL of 1N HCl aqueous solution, twice with 20 mL of saturated aqueous sodium hydrogen carbonate and twice with 20 mL of saturated brine, and dried over magnesium sulfate. After drying, ethyl acetate was distilled off with a rotary evaporator to obtain 15.75 g of a yellow oil.
This was dissolved in a mixed solvent of 140 mL of water and 70 mL of methanol, and extracted five times with 70 mL of heptane. Thereafter, the water-methanol layer was extracted three times with 50 mL of ethyl acetate, and the ethyl acetate layers were combined and dried over magnesium sulfate. After drying, ethyl acetate was distilled off with a rotary evaporator to obtain 9.50 g of crude 3-methacryloyloxy-4-hydroxytetrahydrofuran as a colorless oil (yield based on methacrylic acid chloride: 43.1% by mass). . This was subjected to distillation in a thin film distillation apparatus in which the volatile part temperature was set to 98 ° C.
7.46 g of purified 3-methacryloyloxy-4-hydroxytetrahydrofuran as a colorless oil was obtained from the distilling portion of the thin film distillation (yield based on methacrylic acid chloride: 33.9% by mass, GC purity: 99% by mass). %, GPC purity: 99% by mass).
The instrumental analysis results of the product are shown below.
(1H-NMR (400 MHz), CDCl ₃ , in ppm); 6.19 (1H, brs), 5.66 (1H, brs), 5.21 (1H, br dd), 4.50 (1H, br ddd), 4.12 (1H, dd), 4.00 (1H, dd), 3.88 (1H, dd), 3.75 (1H, dd), 2.12 (1H, brs, OH), 1.98 (3H, s, Me).
(13C-NMR (100 MHz), CDCl ₃ , in ppm); 166.96, 135.59, 126.72, 73.97, 72.39, 71.08, 70.56, 18.26.
GC-mass (measurement after TMS treatment, CI ionization method); M + TMS = 245.
From the above analysis results, it was revealed that the product was 3-methacryloyloxy-4-hydroxytetrahydrofuran.

Resins (A) -1 to (A) -13 were synthesized using the following monomers (1) to (9), and the weight average molecular weight (Mw), dispersity (Mw / Mn), and composition ratio (mol) of each resin. The ratio is shown in Table 1.
The mass average molecular weight (Mw) and dispersity (Mw / Mn) were determined on a polystyrene conversion basis by gel permeation chromatography (GPC). The composition ratio was calculated by carbon NMR. In the chemical formula, the number attached to the lower right of the structural unit indicates the ratio (mol%) of each structural unit in the polymer.

Synthesis example 2
In a flask equipped with a nitrogen inlet, a stirrer, a condenser and a thermometer, under a nitrogen atmosphere, 10 g of compound (1), 200 mL of tetrahydrofuran (THF), polymerization initiator V-601 (trade name, Wako Pure Chemical Industries, Ltd.) 0.6 g) was mixed and refluxed for 6 hours. Thereafter, the reaction solution was dropped into a large amount of heptane while stirring, and the resulting precipitate was filtered off and dried under reduced pressure to obtain Resin (A) -1 (the following chemical formula).

Synthesis example 3
In a nitrogen atmosphere, a flask equipped with a nitrogen inlet, a stirrer, a condenser and a thermometer was charged with 70 g of THF, and the temperature of the hot water bath was raised to 80 ° C. while stirring. 27.6 g of compound (1), 18.9 g of compound (2), 37.5 g of compound (3), 126 g of THF, and 3.2 g of polymerization initiator V-601 (trade name, manufactured by Wako Pure Chemical Industries, Ltd.) The mixed monomer solution was dropped into the flask over 6 hours at a constant rate using a dropping device, and then held at 80 ° C. for 1 hour. Next, the obtained reaction solution was dropped into a large amount of heptane while stirring, and the resulting precipitate was filtered off and dried under reduced pressure to obtain Resin (A) -2 (the following chemical formula).

Synthesis example 4
A flask equipped with a nitrogen inlet, a stirrer, a condenser and a thermometer was charged with 71 g of THF under a nitrogen atmosphere, and the temperature of the hot water bath was raised to 80 ° C. while stirring. 27.6 g of compound (1), 18.9 g of compound (2), 39.7 g of compound (4), 129 g of THF, and 3.2 g of polymerization initiator V-601 (trade name, manufactured by Wako Pure Chemical Industries, Ltd.) The mixed monomer solution was dropped into the flask over 6 hours at a constant rate using a dropping device, and then held at 80 ° C. for 1 hour. Next, the obtained reaction solution was dropped into a large amount of heptane while stirring, and the resulting precipitate was filtered off and dried under reduced pressure to obtain Resin (A) -3 (the following chemical formula).

Synthesis example 5
In a nitrogen atmosphere, a flask equipped with a nitrogen inlet, a stirrer, a condenser, and a thermometer was charged with 80 g of THF, and the temperature of the hot water bath was raised to 80 ° C. while stirring. 27.6 g of compound (1), 18.9 g of compound (2), 49.0 g of compound (5), 144 g of THF, and 3.2 g of polymerization initiator V-601 (trade name, manufactured by Wako Pure Chemical Industries, Ltd.) The mixed monomer solution was dropped into the flask over 6 hours at a constant rate using a dropping device, and then held at 80 ° C. for 1 hour. Next, the obtained reaction solution was dropped into a large amount of heptane while stirring, and the resulting precipitate was filtered off and dried under reduced pressure to obtain Resin (A) -4 (the following chemical formula).

Synthesis Example 6
In a nitrogen atmosphere, a flask equipped with a nitrogen inlet, a stirrer, a condenser and a thermometer was charged with 78 g of THF, and the temperature of the hot water bath was raised to 80 ° C. while stirring. 34.4 g of compound (1), 18.9 g of compound (2), 40.4 g of compound (6), 141 g of THF and 3.2 g of polymerization initiator V-601 (trade name, manufactured by Wako Pure Chemical Industries, Ltd.) The mixed monomer solution was dropped into the flask over 6 hours at a constant rate using a dropping device, and then held at 80 ° C. for 1 hour. Next, the obtained reaction solution was dropped into a large amount of heptane while stirring, and the resulting precipitate was filtered off and dried under reduced pressure to obtain Resin (A) -5 (the following chemical formula).

Synthesis example 7
In a nitrogen atmosphere, a flask equipped with a nitrogen inlet, a stirrer, a condenser and a thermometer was charged with 78 g of THF, and the temperature of the hot water bath was raised to 80 ° C. while stirring. 34.4 g of compound (1), 18.9 g of compound (2), 40.4 g of compound (6), 141 g of THF and 4.5 g of polymerization initiator V-601 (trade name, manufactured by Wako Pure Chemical Industries, Ltd.) The mixed monomer solution was dropped into the flask over 6 hours at a constant rate using a dropping device, and then held at 80 ° C. for 1 hour. Next, the obtained reaction solution was dropped into a large amount of heptane while stirring, and the resulting precipitate was filtered off and dried under reduced pressure to give resin (A) -6 (similar to the above chemical formula (A) -5). Chemical formula) was obtained.

Synthesis example 8
In a nitrogen atmosphere, a flask equipped with a nitrogen inlet, a stirrer, a condenser and a thermometer was charged with 56 g of THF, and the temperature of the hot water bath was raised to 80 ° C. while stirring. 13.8 g of compound (1), 15.7 g of compound (7), 11.4 g of compound (8), 27.2 g of compound (9), 102 g of THF, and polymerization initiator V-601 (trade name, Jun Wako) A monomer solution in which 4.5 g of Yakuhin Kogyo Co., Ltd. was mixed was dropped into the flask over 6 hours at a constant rate using a dropping device, and then kept at 80 ° C. for 1 hour. Next, the obtained reaction solution was dropped into a large amount of heptane while stirring, and the resulting precipitate was filtered off and dried under reduced pressure to obtain Resin (A) -7 (the following chemical formula).

Synthesis Example 9
(Synthesis of Resins (A) -8 to (A) -13)
In the above synthesis example, the following resins (A) -8 to (A) -13 were respectively prepared in the same manner as in the above synthesis example except that the monomer for deriving the structural unit of each resin was used at a predetermined molar ratio. Synthesized.

[Examples 1 to 11, Comparative Example 1]
Each component shown in Table 2 was mixed and dissolved to prepare a resist composition solution (Example 1: Negative resist composition / Examples 2 to 11, Comparative Example 1: Positive resist composition). However, Example 1 is a reference example.

  The meaning of each abbreviation in Table 2 is as follows. Moreover, the numerical value in [] is a compounding quantity (mass part).

(B) -1: Triphenylsulfonium trifluoromethanesulfonate.
(B) -2: Triphenylsulfonium nonafluorobutanesulfonate.
(B) -3: Di (1-naphthyl) phenylsulfonium nonafluorobutanesulfonate.
(B) -4: (4-methylphenyl) diphenylsulfonium nonafluorobutanesulfonate.
(C) -1: Tetramethoxymethylated glycoluril MX270 (product name, manufactured by Sanwa Chemical Co., Ltd.).
(D) -1: Triisopropanolamine.
(D) -2: Triethanolamine.
(D) -3: Tri-n-octylamine.
(E) -1: salicylic acid.
(S) -1: Propylene glycol monomethyl ether (PGME).
(S) -2: Mixed solvent of PGMEA / EL = 8/2 (mass ratio).
(S) -3: PGMEA / PGME = 6/4 (mass ratio) mixed solvent.

The following evaluation was performed using the resist composition solutions of Examples 1-9.
[Formation of resist pattern]
First, an organic antireflection film composition “ARC29” (trade name, manufactured by Brewer Science) is uniformly applied on a silicon wafer using a spinner, and baked on a hot plate at 225 ° C. for 60 seconds to be dried. Thereby, an organic antireflection film having a thickness of 77 nm was formed.
The resist composition solution obtained above is uniformly coated on the antireflection film using a spinner, and prebaked (PAB) for 60 seconds at a temperature shown in Table 3 on a hot plate. Thus, a resist film was formed (see Table 3).
Next, Examples 1 to 8 are ArF exposure apparatus NSR-S302 (Nikon; NA (numerical aperture) = 0.60, 2/3 annular illumination), and Example 9 is ArF exposure apparatus NSR-S306 (Nikon). ArF excimer laser (193 nm) was selectively exposed through a mask pattern (halftone) using NA (numerical aperture) = 0.78, 2/3 annular illumination).
Then, a post-exposure heating (PEB) treatment was performed for 60 seconds at the temperature shown in Table 3, and further developed with an aqueous 2.38 mass% tetramethylammonium hydroxide (TMAH) solution at 23 ° C. for 60 seconds, and then washed with water for 30 seconds. And dried to form a line-and-space (1: 1) resist pattern.

<Sensitivity>
Example 1 The sensitivity (Eop, mJ / cm ² ) at which a line and space pattern (L / S pattern) having a line width of 250 nm and a pitch of 500 nm was formed was measured.
Examples 2 to 8: The sensitivity (Eop, mJ / cm ² ) at which a line and space pattern (L / S pattern) having a line width of 120 nm and a pitch of 240 nm was formed was measured.
Example 9: The sensitivity (Eop, mJ / cm ² ) at which a line and space pattern (L / S pattern) having a line width of 90 nm and a pitch of 180 nm was formed was measured.

<Resolution>
In the Eop, the pattern size was changed, and the limit resolution (nm), which is the minimum dimension of the pattern to be resolved, was obtained. The results are shown in Table 3.

<Line width roughness (LWR)>
In Example 9, the line width of the resist pattern having a line width of 90 nm and a pitch of 180 nm formed in the Eop was measured at five locations in the longitudinal direction of the line by a side length SEM (trade name: S-9220, manufactured by Hitachi, Ltd.). Measurements were made, and from the results, a triple value (3 s) of the standard deviation (s) was calculated as a scale indicating LWR. The smaller the value of 3s, the smaller the roughness of the line width, which means that a resist pattern with a more uniform width was obtained.
As a result, LWR was 5.9 nm, which was a very low value.

From the results of Table 3, it was confirmed that a fine resist pattern could be formed by using the resist compositions of Examples 1 to 9 according to the present invention.
Moreover, it has confirmed that the resist composition of Examples 1-9 concerning this invention can form the resist pattern in which LWR was reduced.

Next, the following evaluation was performed using the positive resist composition solutions of Examples 10 to 11 and Comparative Example 1.
[Formation of resist pattern]
First, an organic antireflection film composition “ARC29” (trade name, manufactured by Brewer Science) is uniformly applied on a silicon wafer using a spinner, and baked on a hot plate at 225 ° C. for 60 seconds to be dried. Thereby, an organic antireflection film having a thickness of 77 nm was formed.
On the antireflection film, the positive resist composition solutions of Examples 10 to 11 and Comparative Example 1 were uniformly applied using a spinner, and on a hot plate at a temperature shown in Tables 4 and 5 for 60 seconds. A resist film having a thickness of 120 nm was formed by performing pre-baking (PAB) treatment.
Next, an ArF excimer laser (193 nm) was selectively exposed through a mask pattern (halftone) by the following exposure apparatuses and conditions (1) and (2).
(1) NSR-S306; NA (numerical aperture) = 0.78, 2/3 annular illumination (2) ASML 1400; NA (numerical aperture) = 0.93, sigma C-Quad
Then, a post-exposure heating (PEB) treatment for 60 seconds at the temperatures shown in Tables 4 and 5 was performed, followed by development with an aqueous 2.38 mass% tetramethylammonium hydroxide (TMAH) solution at 23 ° C. for 30 seconds, followed by 30 It was washed with water for 2 seconds and dried to form a line and space (1: 1) resist pattern.

In the case of the exposure apparatus and conditions of (1).
<Sensitivity>
The sensitivity (Eop, mJ / cm ² ) at which a line and space pattern (L / S pattern) having a line width of 80 nm and a pitch of 160 nm was formed was measured.

<Line width roughness (LWR)>
LWR (nm) was calculated by the same method as described above for a resist pattern formed in Eop with a line width of 80 nm and a pitch of 160 nm. The results are shown in Table 4.

<Collapse Margin>
In L / S pattern formation with a line width of 80 m and a pitch of 160 nm as targets, the SEM shows where pattern collapse occurs when the exposure time in selective exposure is gradually increased and the exposure amount is made larger than Eop. It was observed by (scanning electron microscope).
At that time, let T be the exposure amount when pattern collapse starts to occur, and the following equation collapse margin (unit:%) = (T / Eop) × 100
The fall margin was calculated. The results are shown in Table 4.

In the case of (2) exposure apparatus and conditions.
<Sensitivity>
The sensitivity (Eop, mJ / cm ² ) at which a line and space pattern (L / S pattern) having a line width of 60 nm and a pitch of 120 nm was formed was measured.

<Line width roughness (LWR)>
LWR (nm) was calculated by the same method as described above for a resist pattern with a line width of 60 nm and a pitch of 120 nm formed in the Eop. The results are shown in Table 5.

<Mask error factor (MEF)>
In the above Eop, the mask error factor was calculated when the pitch was fixed at 120 nm and the mask size was changed to 57, 58, 59, 60, 61, 62 nm and the L / S pattern was formed.
The numerical value of the mask error factor is obtained by plotting the line width (nm) targeted by the mask pattern on the horizontal axis and the actual line width (nm) of the L / S pattern formed on the vertical axis. Is the slope of The closer the mask error factor is to 1, the more the resist pattern faithful to the mask pattern is formed. The results are shown in Table 5.

<Depth of focus (DOF)>
In the above Eop, the focal point is appropriately shifted up and down, and the L / S pattern can be formed within the range of the dimensional change rate of the target dimension of 60 nm ± 10% (ie, 54 to 66 nm) (DOF, unit: nm). Asked. The results are shown in Table 5.

From the results of Tables 4 and 5, it was confirmed that a fine resist pattern could be formed by using the positive resist compositions of Examples 10 to 11 according to the present invention.
In addition, the positive resist compositions of Examples 10 to 11 according to the present invention have the same LWR level and good collapse margin as compared with the positive resist composition of Comparative Example 1 different from the present invention. I was able to confirm.
In addition, it can be confirmed that the positive resist composition of Example 10 according to the present invention is superior in LWR, MEF and DOF as compared with the positive resist composition of Comparative Example 1 which is different from the present invention. It was.

Claims (3)

The following general formula (a-0)

[Wherein, R represents a hydrogen atom, a halogen atom, a halogen Kaa alkyl group of 1 to 5 alkyl groups or carbon atoms of 1 to 5 carbon atoms; a is an integer from 0 to 2; b is 1 C is an integer of 3; c is an integer of 1 to 2; a + b is an integer of 2 or more. ]
And the structural unit (a1) derived from an acrylate ester containing an acid dissociable, dissolution inhibiting group, and the alkali solubility is increased by the action of an acid. Resin resin.   The resist resin according to claim 1, wherein the structural unit (a0) is 3-methacryloyloxy-4-hydroxytetrahydrofuran.   The resist resin according to claim 1, further comprising a structural unit (a3) derived from an acrylate ester containing a polar group-containing aliphatic hydrocarbon group, which does not correspond to the structural unit (a0).