JP2002161116A - Polymer compound, resist material, and pattern forming method - Google Patents

Abstract

(57) Abstract: A polymer having a weight average molecular weight of 1,000 to 500,000, comprising a repeating unit represented by the following general formula (1-1) or (1-2): Compound. Embedded image (In the formula, k is 0 or 1. m is 0, 1, 2, 3 or 4. n is 1 or 2.) Resist using the polymer compound of the present invention as a base resin. Since the material is sensitive to high energy rays and has excellent sensitivity, resolution, and etching resistance, it is useful for fine processing using electron beams or far ultraviolet rays. In particular, since the absorption at the exposure wavelength of an ArF excimer laser or a KrF excimer laser is small, a fine pattern perpendicular to the substrate can be easily formed.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to (1) a polymer compound containing a specific repeating unit, (2) a resist material containing the polymer compound as a base resin, and (3) a resist material containing the polymer compound. A pattern forming method.

[0002]

2. Description of the Related Art In recent years, as the integration and speed of LSIs have been increased and the pattern rules have been required to be finer, far-ultraviolet lithography has been regarded as a promising next-generation fine processing technology. Among them, KrF excimer laser light, A
Photolithography using an rF excimer laser beam as a light source is required to be realized as a technology indispensable for ultrafine processing of 0.3 μm or less.

In a resist material for a KrF excimer laser, polyhydroxystyrene, which has both practically usable transparency and etching resistance, has become a practically standard base resin. In the case of resist materials for ArF excimer lasers, materials such as polyacrylic acid or polymethacrylic acid derivatives and high molecular weight compounds containing an aliphatic cyclic compound in the main chain have been studied, but all have advantages and disadvantages. Yes, the standard base resin has not yet been determined.

That is, a resist material using a derivative of polyacrylic acid or polymethacrylic acid has advantages such as high reactivity of an acid-decomposable group and excellent substrate adhesion. Although relatively good results are obtained, the etching resistance is extremely low due to the soft main chain of the resin, which is not practical. On the other hand, in the case of a resist material using a polymer compound containing an aliphatic cyclic compound in the main chain, although the etching resistance is at a practical level because the main chain of the resin is sufficiently rigid, the reactivity of the acid-decomposable protecting group is high. Is inferior to acrylics, resulting in low sensitivity and low resolution, and the main chain of the resin is too rigid, resulting in poor substrate adhesion, which is also not suitable. As pattern rules are required to be further miniaturized, resist materials that exhibit excellent performance in all of sensitivity, resolution, and etching resistance are required.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and (1) a polymer compound having excellent reactivity, rigidity and substrate adhesion; It is another object of the present invention to provide a resist material having resolution and etching resistance which are significantly higher than those of conventional products, and (3) a pattern forming method using the resist material.

[0006]

Means for Solving the Problems and Embodiments of the Invention The present inventors have made intensive studies in order to achieve the above object, and as a result, have obtained the following general formula (1-
The novel polymer compound having a weight average molecular weight of 1,000 to 500,000 containing the repeating unit represented by 1) or (1-2) is excellent in reactivity, rigidity and substrate adhesion. It has been found that the resist material used as the obtained base resin has high resolution and high etching resistance, and that this resist material is extremely effective for precise fine processing.

That is, the present invention provides the following polymer compound. [I] A polymer having a weight average molecular weight of 1,000 to 500,000, containing a repeating unit represented by the following general formula (1-1) or (1-2).

Embedded image (In the formula, k is 0 or 1. m is 0, 1, 2, 3, or 4. n is 1 or 2.)

[II] The composition according to [I], further comprising a repeating unit represented by the following general formula (2-1) in addition to the repeating unit represented by the above general formula (1-1). Molecular compound.

Embedded image (In the formula, k is the same as above. R ¹ represents a hydrogen atom, a methyl group or CH ₂ CO ₂ R ^3. R ² represents a hydrogen atom, a methyl group or CO ₂ R ^3. R ³ is a carbon atom. R ⁴ represents an acid labile group, R ⁵ represents a halogen atom, a hydroxyl group, a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms. Cyclic alkoxy group, acyloxy group, alkylsulfonyloxy group,
Or a linear, branched, or cyclic alkoxyalkoxy group or an alkoxycarbonyloxy group having 2 to 15 carbon atoms, in which part or all of the hydrogen atoms on the constituent carbon atoms may be substituted with halogen atoms. Z is a single bond or a linear, branched or cyclic (p +
2) a valent hydrocarbon group, and when it is a hydrocarbon group, one or more methylene groups may be substituted with an oxygen atom to form a chain or cyclic ether; One hydrogen atom may be replaced by an oxygen atom to form a ketone. p is 0, 1 or 2. )

[III] In addition to the repeating unit represented by the above general formula (1-1), the above [I] comprises repeating units represented by the following general formulas (2-1) and (3). 8. The polymer compound according to item 1.

Embedded image (In the formula, k, p, and R ^{1 to} R ⁵ are the same as described above.)

[IV] In addition to the repeating unit represented by the general formula (1-1), a repeating unit represented by the following general formula (4) or a repeating unit represented by the following general formula (2-1) A repeating unit represented by the formula (4);
The polymer compound according to [I], comprising a repeating unit represented by the following general formula (3).

Embedded image (In the formula, k, p, and R ^{1 to} R ⁵ are the same as described above.)

[V] In addition to the repeating unit represented by the general formula (1-2), the repeating unit represented by the following general formula (2-2) is contained. Molecular compound.

Embedded image (In the formula, k, p, and R ^{1 to} R ⁵ are the same as described above.)

Further, the present invention provides the following resist material. [VI] A resist material comprising the polymer compound according to any one of [I] to [V].

Further, the present invention provides the following pattern forming method. [VII] a step of applying the resist material according to [VI] on a substrate, a step of exposing with a high-energy ray or an electron beam through a photomask after the heat treatment, and, if necessary, a heat treatment and then a development. And developing with a liquid.

The high molecular compound containing a repeating unit represented by the general formula (1-1) or (1-2) has a high rigidity because it contains an alicyclic ring having a crosslink in the main chain. . In addition, since it has a highly polar 5- or 6-membered lactone structure, it has excellent substrate adhesion. In addition, a spacer having an appropriate length introduced between the lactone structure and the rigid main chain appropriately moderates the rigidity which was conventionally excessive, and the lactone structure portion is disposed away from the main chain. As a result, it has become more effective as a polar group, and as a result, it has much higher substrate adhesion than conventional products. In addition, low reactivity, which was a bigger problem than in the past, was improved by increasing the diffusivity of the generated acid by the effect of introducing the spacer, and at the same time, the line edge roughness was reduced. Therefore, a resist material using this polymer compound as a base resin has excellent performance in all of sensitivity, resolution and etching resistance, and is extremely useful for forming a fine pattern.

Hereinafter, the present invention will be described in more detail.
The novel polymer compound of the present invention contains a repeating unit represented by the following general formula (1-1) or (1-2), and has a weight average molecular weight of 1,000 to 500,000.
belongs to.

[0016]

Embedded image (In the formula, k is 0 or 1. m is 0, 1, 2, 3, or 4. n is 1 or 2.)

Further, the polymer compound of the present invention may be more specifically the following four types. (1) Those containing a repeating unit represented by the following general formula (2-1) in addition to a repeating unit represented by the above general formula (1-1).

[0018]

Embedded image (In the formula, k is the same as above. R ¹ represents a hydrogen atom, a methyl group or CH ₂ CO ₂ R ^3. R ² represents a hydrogen atom, a methyl group or CO ₂ R ^3. R ³ is a carbon atom. R ⁴ represents an acid labile group, R ⁵ represents a halogen atom, a hydroxyl group, a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms. Cyclic alkoxy group, acyloxy group, alkylsulfonyloxy group,
Or a linear, branched, or cyclic alkoxyalkoxy group or an alkoxycarbonyloxy group having 2 to 15 carbon atoms, in which part or all of the hydrogen atoms on the constituent carbon atoms may be substituted with halogen atoms. Z is a single bond or a linear, branched or cyclic (p +
2) a valent hydrocarbon group, and when it is a hydrocarbon group, one or more methylene groups may be substituted with an oxygen atom to form a chain or cyclic ether; One hydrogen atom may be replaced by an oxygen atom to form a ketone. p is 0, 1 or 2. )

(2) Those containing the repeating units represented by the following general formulas (2-1) and (3) in addition to the repeating units represented by the above general formula (1-1).

[0020]

Embedded image (In the formula, k, p, and R ^{1 to} R ⁵ are the same as described above.)

(3) In addition to the repeating unit represented by the general formula (1-1), a repeating unit represented by the following general formula (4) or a repeating unit represented by the following general formula (2-1) and One containing a repeating unit represented by the formula (4) and a repeating unit represented by the following general formula (3).

[0022]

Embedded image (In the formula, k, p, and R ^{1 to} R ⁵ are the same as described above.)

(4) Those containing a repeating unit represented by the following general formula (2-2) in addition to a repeating unit represented by the above general formula (1-2).

[0024]

Embedded image (In the formula, k, p, and R ^{1 to} R ⁵ are the same as described above.)

Here, R ¹ is a hydrogen atom, a methyl group or C
H ₂ CO ₂ R ³ is shown. Specific examples of R ³ will be described later.
R ² represents a hydrogen atom, a methyl group or CO ₂ R ³ . R ³ represents a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and tert. -Butyl group, tert-amyl group, n-pentyl group, n-hexyl group, cyclopentyl group, cyclohexyl group, ethylcyclopentyl group, butylcyclopentyl group, ethylcyclohexyl group, butylcyclohexyl group, adamantyl group, ethyladamantyl group, butyladamantyl And the like. R ⁴ represents an acid labile group, and specific examples thereof will be described later. R ⁵ is a halogen atom, a hydroxyl group, of the straight, branched or cyclic alkoxy group, an acyloxy group, alkylsulfonyloxy group, or a C 2-15 linear, branched or cyclic Shows an alkoxyalkoxy group or an alkoxycarbonyloxy group, and a part or all of the hydrogen atoms on the constituent carbon atoms may be substituted with a halogen atom.Specifically, fluorine, chlorine, bromine, a methoxy group, an ethoxy group, Propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, t
ert-amyloxy group, n-pentoxy group, n-hexyloxy group, cyclopentyloxy group, cyclohexyloxy group, ethylcyclopentyloxy group, butylcyclopentyloxy group, ethylcyclohexyloxy group,
Butylcyclohexyloxy group, adamantyloxy group, ethyladamantyloxy group, butyladamantyloxy group, formyloxy group, acetoxy group, ethylcarbonyloxy group, pivaloyloxy group, methoxycarbonyloxy group, ethoxycarbonyloxy group, te
rt-butoxycarbonyloxy group, methanesulfonyloxy group, ethanesulfonyloxy group, n-butanesulfonyloxy group, trifluoroacetoxy group, trichloroacetoxy group, 3,3,3-trifluoroethylcarbonyloxy group, methoxymethoxy group, 1-ethoxyethoxy group, 1-ethoxypropoxy group, 1-te
rt-butoxyethoxy group, 1-cyclohexyloxyethoxy group, 2-tetrahydrofuranyloxy group, 2-
Examples thereof include a tetrahydropyranyloxy group. Z represents a single bond or a linear, branched, or cyclic (p + 2) -valent hydrocarbon group having 1 to 5 carbon atoms, and when it is a hydrocarbon group, one or more methylene groups are substituted with an oxygen atom. It may be substituted to form a chain or cyclic ether, or two hydrogen atoms on the same carbon may be substituted with an oxygen atom to form a ketone. For example, when p = 0, Specifically, methylene, ethylene, trimethylene, tetramethylene, pentamethylene, 1,2-propanediyl, 1,3-butanediyl, 1-oxo-2-oxapropane-1,3-diyl, 3-methyl-1-oxo -2-oxabutane-
1,4-diyl and the like can be exemplified, and when p is other than 0,
Examples thereof include (p + 2) -valent groups excluding p hydrogen atoms from the above specific examples.

As the acid labile group for R ⁴ , various types can be used. Specifically, the following formulas (L1) to (L)
Group represented by 4), having 4 to 20 carbon atoms, preferably 4 to 1 carbon atoms
5 tertiary alkyl groups, each alkyl group having 1 carbon atom
And an oxoalkyl group having 4 to 20 carbon atoms.

[0027]

Embedded image

Here, a chain line indicates a bond (the same applies hereinafter). In the formula, R ^L01 and R ^L02 represent a hydrogen atom or a carbon number of 1 to 1.
8, preferably 1 to 10 linear, branched or cyclic alkyl groups, specifically methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert- Examples thereof include a butyl group, a cyclopentyl group, a cyclohexyl group, a 2-ethylhexyl group, and an n-octyl group. R ^L03 has 1 to 18 carbon atoms, preferably 1
Represents a monovalent hydrocarbon group which may have a hetero atom such as 10 to 10 oxygen atoms, a linear, branched or cyclic alkyl group, a part of these hydrogen atoms is a hydroxyl group, an alkoxy group,
Examples thereof include those substituted with an oxo group, an amino group, an alkylamino group, and the like, and specific examples include the following substituted alkyl groups.

[0029]

Embedded image

R ^L01 and R ^L02 , R ^L01 and R ^L03 , R ^L02 and R
^L03 and ^R03 may be bonded to each other to form a ring, and when forming a ring, R ^L01 , R ^L02 and R ^L03 each have 1 carbon atom.
-18, preferably 1-10, linear or branched alkylene groups.

R ^L04 has 4 to 20 carbon atoms, preferably 4 to 20 carbon atoms.
15 tertiary alkyl groups, each alkyl group is a trialkylsilyl group having 1 to 6 carbon atoms, an oxoalkyl group having 4 to 20 carbon atoms or a group represented by the above formula (L1), Specifically, tert-butyl group, tert-amyl group, 1,1-diethylpropyl group, 2-cyclopentylpropan-2-yl group, 2-
Cyclohexylpropan-2-yl group, 2- (bicyclo [2.2.1] heptane-2-yl) propan-2-yl group, 2- (adamantan-1-yl) propan-2-
Yl group, 1-ethylcyclopentyl group, 1-butylcyclopentyl group, 1-ethylcyclohexyl group, 1-butylcyclohexyl group, 1-ethyl-2-cyclopentenyl group, 1-ethyl-2-cyclohexenyl group, 2-methyl -2-adamantyl group, 2-ethyl-2-adamantyl group, and the like. Specific examples of the trialkylsilyl group include a trimethylsilyl group, a triethylsilyl group, and a dimethyl-tert-butylsilyl group. Specific examples of the group include a 3-oxocyclohexyl group, a 4-methyl-2-oxooxan-4-yl group, a 5-methyl-2-oxooxolan-5-yl group, and the like. y is an integer of 0-6.

R ^L05 represents a monovalent hydrocarbon group which may contain a heteroatom having 1 to 8 carbon atoms or an aryl group which may be substituted and has 6 to 20 carbon atoms. Specific examples of the hydrocarbon group include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, and ter
t-amyl group, n-pentyl group, n-hexyl group, cyclopentyl group, linear or branched or cyclic alkyl group such as cyclohexyl group, some of these hydrogen atoms are hydroxyl, alkoxy, carboxy, Examples thereof include those substituted with an alkoxycarbonyl group, an oxo group, an amino group, an alkylamino group, a cyano group, a mercapto group, an alkylthio group, a sulfo group, and the like.Specific examples of the optionally substituted aryl group include: Represents a phenyl group, a methylphenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group or the like. m is 0 or 1, n is 0, 1,
It is either 2 or 3, and is a number that satisfies 2m + n = 2 or 3.

[0033] R ^L06 represents a optionally substituted aryl group having from 6 to 20 carbon hydrocarbon radical or carbon also may monovalent contain a hetero atom having 1 to 8 carbon atoms, like in particular the R ^L05 And the like. R ^{L07 to} R ^L16 each independently represent a hydrogen atom or a monovalent hydrocarbon group which may contain a heteroatom having 1 to 15 carbon atoms, specifically, a methyl group,
Ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, tert
-Amyl group, n-pentyl group, n-hexyl group, n-octyl group, n-nonyl group, n-decyl group, cyclopentyl group, cyclohexyl group, cyclopentylmethyl group, cyclopentylethyl group, cyclopentylbutyl group, cyclohexylmethyl group Linear, branched or cyclic alkyl groups such as cyclohexylethyl group and cyclohexylbutyl group, and some of these hydrogen atoms are hydroxyl, alkoxy, carboxy, alkoxycarbonyl, oxo, amino, alkylamino And those substituted with a group, a cyano group, a mercapto group, an alkylthio group, a sulfo group, or the like. R ^{L07 to} R ^L16 may be bonded to each other to form a ring (for example, R ^L07 and R ^L08 , R ^L07 and R ^L09 , R ^L08 and R ^L10 , R ^L09 and R ^L10 , R ^L11 and R ^L12. ,
^RL13 and ^RL14 ), in which case, a divalent hydrocarbon group which may contain a heteroatom having 1 to 15 carbon atoms is shown. One in which one atom is removed can be exemplified. In addition, R ^{L07 to} R ^L16
Binds without anything intervening in between those bonded to the adjacent carbon may also form a double bond (e.g., R ^L07 and R ^L09, R ^L09 and R ^L15, R ^L13 and R ^L15 and the like).

Specific examples of the linear or branched acid labile groups represented by the formula (L1) include the following groups.

[0035]

Embedded image

As the cyclic group among the acid labile groups represented by the formula (L1), specifically, tetrahydrofuran-2-yl group, 2-methyltetrahydrofuran-2-yl group, tetrahydropyran-2-yl And 2-methyltetrahydropyran-2-yl group.

Specific examples of the acid labile group of the above formula (L2) include a tert-butoxycarbonyl group and a tert-butoxycarbonyl group.
Butoxycarbonylmethyl group, tert-amyloxycarbonyl group, tert-amyloxycarbonylmethyl group, 1,1-diethylpropyloxycarbonyl group,
1,1-diethylpropyloxycarbonylmethyl group,
1-ethylcyclopentyloxycarbonyl group, 1-ethylcyclopentyloxycarbonylmethyl group, 1-ethyl-2-cyclopentenyloxycarbonyl group, 1-
Examples thereof include an ethyl-2-cyclopentenyloxycarbonylmethyl group, a 1-ethoxyethoxycarbonylmethyl group, a 2-tetrahydropyranyloxycarbonylmethyl group, and a 2-tetrahydrofuranyloxycarbonylmethyl group.

Specific examples of the acid labile group of the above formula (L3) include 1-methylcyclopentyl, 1-ethylcyclopentyl, 1-n-propylcyclopentyl, 1-isopropylcyclopentyl, 1-n-butylcyclopentyl, -Sec-butylcyclopentyl, 1-cyclohexylcyclopentyl, 1- (4-methoxy-n-butyl) cyclopentyl, 1-methylcyclohexyl, 1-
Ethylcyclohexyl, 3-methyl-1-cyclopenten-3-yl, 3-ethyl-1-cyclopenten-3-
Yl, 3-methyl-1-cyclohexen-3-yl, 3
-Ethyl-1-cyclohexen-3-yl and the like. The following groups can be specifically exemplified as the acid labile group of the formula (L4).

[0039]

Embedded image

A tertiary alkyl group having 4 to 20 carbon atoms;
As each alkyl group is a trialkylsilyl group having 1 to 6 carbon atoms and an oxoalkyl group having 4 to 20 carbon atoms,
Specific examples include those similar to those described for ^RL04 .

Specific examples of the repeating unit represented by the above general formula (1-1) are shown below, but the present invention is not limited thereto.

[0042]

Embedded image

Specific examples of the repeating unit represented by the above general formula (1-2) are shown below, but the present invention is not limited thereto.

[0044]

Embedded image

Specific examples of the repeating unit represented by the above general formula (2-1) are shown below, but the present invention is not limited thereto.

[0046]

Embedded image

Specific examples of the repeating unit represented by the above general formula (2-2) are shown below, but the present invention is not limited thereto.

[0048]

Embedded image

Specific examples of the repeating unit represented by the general formula (4) are shown below, but the present invention is not limited thereto.

[0050]

Embedded image

The polymer compound of the present invention may further contain, if necessary, one or more kinds selected from the repeating units represented by the following formulas (M1) to (M8-2). Good.

[0052]

Embedded image (Wherein, R ⁰⁰¹ is a hydrogen atom, a methyl group or CH ₂ CO ₂ R
⁰⁰³ is shown. R ⁰⁰² is a hydrogen atom, a methyl group or CO ₂ R ⁰⁰³
Is shown. R ⁰⁰³ represents a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms. R ⁰⁰⁴ represents a hydrogen atom or a monovalent hydrocarbon group having a carboxy group or a hydroxyl group having 1 to 15 carbon atoms. At least one of R ^{005 to} R ⁰⁰⁸ represents a carboxy group having 1 to 15 carbon atoms or a monovalent hydrocarbon group containing a hydroxyl group, and the rest are each independently a hydrogen atom or a linear group having 1 to 15 carbon atoms; It represents a branched or cyclic alkyl group. R ^{005 to} R ⁰⁰⁸ may form a ring with each other, in which case at least one of R ^{005 to} R ⁰⁰⁸ is a divalent hydrocarbon group having a carboxy group or a hydroxyl group having 1 to 15 carbon atoms. And the rest each independently represent a single bond or a linear, branched or cyclic alkylene group having 1 to 15 carbon atoms. R ⁰⁰⁹ represents a monovalent hydrocarbon group having a —CO ₂ — partial structure having 3 to 15 carbon atoms. R ⁰¹⁰ to R ⁰¹ at least one ³ -CO ₂ of 2 to 15 carbon atoms - a monovalent hydrocarbon group containing a partial structure, linear hydrogen atom or 1 to 15 carbon atoms in each remaining independently It represents a chain, branched or cyclic alkyl group. R ^{010 to} R ⁰¹³ may form a ring with each other, in which case at least one of R ^{010 to} R ⁰¹³ is a divalent hydrocarbon containing a —CO ₂ — partial structure having 1 to 15 carbon atoms. And the rest each independently represent a single bond or a linear, branched or cyclic alkylene group having 1 to 15 carbon atoms. R ⁰¹⁴ represents a polycyclic hydrocarbon group having 7 to 15 carbon atoms or an alkyl group containing a polycyclic hydrocarbon group. R ⁰¹⁵ represents an acid labile group. X represents CH ₂ or an oxygen atom. k is 0 or 1. )

Here, R ⁰⁰¹ represents a hydrogen atom, a methyl group or CH ₂ CO ₂ R ⁰⁰³ . A specific example of ^R003 will be described later. R ⁰⁰² represents a hydrogen atom, a methyl group or CO ₂ R ⁰⁰³ . R ⁰⁰³ represents a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms, specifically, a methyl group, an ethyl group,
Propyl group, isopropyl group, n-butyl group, sec-
Butyl group, tert-butyl group, tert-amyl group,
n-pentyl group, n-hexyl group, cyclopentyl group,
Examples thereof include a cyclohexyl group, an ethylcyclopentyl group, a butylcyclopentyl group, an ethylcyclohexyl group, a butylcyclohexyl group, an adamantyl group, an ethyladamantyl group, and a butyladamantyl group. R ⁰⁰⁴ represents a hydrogen atom or a monovalent hydrocarbon group having a carboxy group having 1 to 15 carbon atoms or a hydroxyl group, specifically, carboxyethyl, carboxybutyl, carboxycyclopentyl, carboxycyclohexyl, carboxynorbornyl, carboxy Adamantyl, hydroxyethyl, hydroxybutyl, hydroxycyclopentyl, hydroxycyclohexyl, hydroxynorbornyl, hydroxyadamantyl and the like can be exemplified. At least one of R ^{005 to} R ⁰⁰⁸ represents a carboxy group having 1 to 15 carbon atoms or a monovalent hydrocarbon group containing a hydroxyl group, and the rest are each independently a hydrogen atom or a linear group having 1 to 15 carbon atoms; It represents a branched or cyclic alkyl group. Specific examples of the monovalent hydrocarbon group having a carboxy group or a hydroxyl group having 1 to 15 carbon atoms include carboxy, carboxymethyl, carboxyethyl, carboxybutyl, hydroxymethyl, hydroxyethyl, hydroxybutyl, and 2-carboxyethoxy. Carbonyl, 4-carboxybutoxycarbonyl, 2-hydroxyethoxycarbonyl, 4-hydroxybutoxycarbonyl, carboxycyclopentyloxycarbonyl, carboxycyclohexyloxycarbonyl, carboxynorbornyloxycarbonyl, carboxyadamantyloxycarbonyl, hydroxycyclopentyloxycarbonyl, hydroxycyclohexyloxy Carbonyl, hydroxynorbornyloxycarbonyl,
Examples thereof include hydroxyadamantyloxycarbonyl and the like. Examples of the straight, branched, the alkyl group of cyclic, specifically exemplified the same ones as exemplified for R ^003. R ^{005 to} R ⁰⁰⁸ may form a ring with each other, in which case at least one of R ^{005 to} R ⁰⁰⁸
Represents a divalent hydrocarbon group containing a carboxy group or a hydroxyl group having 1 to 15 carbon atoms, and the rest each independently represent a single bond or a linear, branched or cyclic alkylene group having 1 to 15 carbon atoms. Show. Specific examples of the divalent hydrocarbon group having a carboxy group or a hydroxyl group having 1 to 15 carbon atoms include one hydrogen atom from those exemplified as the monovalent hydrocarbon group having a carboxy group or a hydroxyl group. Excluded ones can be exemplified. Specific examples of the linear, branched, or cyclic alkylene group having 1 to 15 carbon atoms include those exemplified for R ³ with one hydrogen atom removed.

R ⁰⁰⁹ represents a monovalent hydrocarbon group having a —CO ₂ — partial structure having 3 to 15 carbon atoms.
Oxooxolan-3-yl, 4,4-dimethyl-2-
Examples include oxooxolan-3-yl, 4-methyl-2-oxooxan-4-yl, 2-oxo-1,3-dioxolan-4-ylmethyl, 5-methyl-2-oxooxolan-5-yl, and the like. it can. At least one of R ^{010 to} R ^{013 represents} a monovalent hydrocarbon group having a —CO ₂ — partial structure having 2 to 15 carbon atoms, and the rest are each independently a hydrogen atom or a linear chain having 1 to 15 carbon atoms. A branched, branched or cyclic alkyl group. Specific examples of the monovalent hydrocarbon group having a —CO ₂ — partial structure having 2 to 15 carbon atoms include 2-
Oxooxolan-3-yloxycarbonyl, 4,4
-Dimethyl-2-oxooxolan-3-yloxycarbonyl, 4-methyl-2-oxooxan-4-yloxycarbonyl, 2-oxo-1,3-dioxolan-4-ylmethyloxycarbonyl, 5-methyl- 2-
Oxooxolan-5-yloxycarbonyl and the like can be exemplified. Examples of the straight, branched, the alkyl group of cyclic, specifically exemplified the same ones as exemplified for R ^003. R ^{010 to} R ⁰¹³ may form a ring with each other, in which case at least one of R ^{010 to} R ⁰¹³ is a divalent hydrocarbon containing a —CO ₂ — partial structure having 1 to 15 carbon atoms. And the rest each independently represent a single bond or a linear, branched, or cyclic alkylene group having 1 to 15 carbon atoms. Specific examples of the divalent hydrocarbon group having a —CO ₂ — partial structure having 1 to 15 carbon atoms include 1-oxo-2-oxapropane-1,3-diyl, 1,3-
Dioxo-2-oxapropane-1,3-diyl, 1-
Oxo-2-oxabutane-1,4-diyl, 1,3-
In addition to dioxo-2-oxabutane-1,4-diyl,
The -CO ₂ - a monovalent hydrogen atom from those exemplified in the hydrocarbon group containing a partial structure can be exemplified one eliminated therefrom. Specific examples of the linear, branched, or cyclic alkylene group having 1 to 15 carbon atoms include those exemplified for R ⁰⁰³ with one hydrogen atom removed.

R ⁰¹⁴ represents a polycyclic hydrocarbon group having 7 to 15 carbon atoms or an alkyl group containing a polycyclic hydrocarbon group;
Specific examples include norbornyl, bicyclo [3.3.1] nonyl, tricyclo [5.2.1.0 ^2,6 ] decyl, adamantyl, ethyladamantyl, butyladamantyl, norbornylmethyl, adamantylmethyl and the like. . R ⁰¹⁵ represents an acid labile group, and specific examples thereof include the same as those described in the above description. X represents CH ₂ or an oxygen atom. k is 0 or 1.

The repeating units represented by the general formulas (M1) to (M8-2) impart various properties such as developer affinity, substrate adhesion, and etching resistance when used as a resist material. By appropriately adjusting the content of these repeating units, the performance of the resist material can be finely adjusted.

The polymer of the present invention has a weight average molecular weight of 1,000 to 500,000, preferably 3.0 to 500,000.
00 to 100,000. Outside of this range, the etching resistance may be extremely reduced, or the difference in dissolution rate before and after exposure may not be ensured, resulting in reduced resolution.

In the production of the polymer compound of the present invention, a compound represented by the following general formula (1a) is used as a first monomer, and a compound selected from the compounds represented by the following general formulas (2a) to (4a) is used. To 3 to the second to fourth monomers, and, if necessary, one or more of the compounds represented by the following general formulas (M1a) to (M8a) to the subsequent monomers. It can be carried out by the copolymerization reaction used.

[0059]

Embedded image (In the formula, k, p, m, n, and R ^{1 to} R ⁵ are the same as described above.)

[0060]

Embedded image (In the formula, k, R ^{001 to} R ⁰¹⁵ , and X are the same as described above.)

In the copolymerization reaction, by appropriately adjusting the proportion of each monomer, it is possible to obtain a polymer compound capable of exhibiting preferable performance when used as a resist material.

In this case, the polymer compound of the present invention comprises: (i) a monomer of the above formula (1a); (ii) a monomer of the above formulas (2a) to (4a); To (M8a), and (iv) a monomer containing a carbon-carbon double bond other than the above (i) to (iii), for example, methyl methacrylate,
Substituted acrylic esters such as methyl crotonate, dimethyl maleate and dimethyl itaconate; unsaturated carboxylic acids such as maleic acid, fumaric acid and itaconic acid; substituted norbornenes such as norbornene and methyl norbornene-5-carboxylate; anhydrous Unsaturated acid anhydrides such as itaconic acid and other monomers may be copolymerized.

In the polymer compound of the present invention, a preferable content ratio of each repeating unit based on each monomer can be, for example, in the following range (mol%), but is not limited thereto. . (I) When the polymer compound contains a repeating unit represented by the general formula (1-1) and a repeating unit represented by the above (2-1), the monomer represented by the formula (1a) 1 to 90%, preferably 5 to 80%, more preferably 10 to 70% of the repeating unit represented by the formula (1-1) based on the formula (2-1): 1 to 90%, preferably 5 to 80%, more preferably 10 to 70% of the repeating unit represented by the formula (M5a) to the formula (M5) based on the monomers of the formulas (M5a) to (M8a).
-1) to (M8-1) represented by 0 to 5
0%, preferably 0-40%, more preferably 0-30
%, A repeating unit based on another monomer is 0 to 50%,
Preferably, it can be contained in an amount of 0 to 40%, more preferably 0 to 30%. (II) In the case where the polymer compound contains a repeating unit represented by the general formula (1-1), a repeating unit represented by (2-1), and a repeating unit represented by (3) 1 to 49%, preferably 3 to 45%, more preferably 5 to 40% of the repeating unit represented by the formula (1-1) based on the monomer of the formula (1a), 1 to 49%, preferably 3 to 45%, more preferably 5 to 40% of the repeating unit represented by the formula (2-1) based on the body, in the formula (3) based on the monomer of the formula (3a) The repeating unit represented by the formula (M5a) is based on a monomer represented by the formula (M5a) to (M8a).
-1) to 0 to 2 (M8-1)
5%, preferably 0-20%, more preferably 0-15
%, A repeating unit based on another monomer is 0 to 25%,
Preferably, it can be contained in an amount of 0 to 20%, more preferably 0 to 15%. (III) a polymer compound wherein the repeating unit represented by the general formula (1-1) and the repeating unit represented by the above (4) or the repeating unit represented by the above (2-1) and the repeating unit represented by the above (4) And a repeating unit represented by formula (1a) based on the monomer represented by formula (1a): 1 to 49%, preferably 3 to 49%. 45%, more preferably 5 to 40%, 0 to 40%, preferably 0 to 35%, more preferably 0 to 40% of the repeating unit represented by the formula (2-1) based on the monomer of the formula (2a) 30%, 1 to 80%, preferably 1 to 70%, more preferably 1 to 50% of the repeating unit represented by the formula (4) based on the monomer of the formula (4a); 1-49%, preferably a repeating unit represented by the formula (3) based on a body 5 to 45%, more preferably 10 to 40%, the formula (M) based on the monomers of the formulas (M1a) to (M8a)
1) to a repeating unit represented by (M8-1) of 0 to 25
%, Preferably 0 to 20%, more preferably 0 to 15%
%, A repeating unit based on another monomer is 0 to 25%,
Preferably, it can be contained in an amount of 0 to 20%, more preferably 0 to 15%. (IV) When the polymer compound contains a repeating unit represented by the general formula (1-2) and a repeating unit represented by the above (2-2), the monomer represented by the formula (1a) 1 to 90%, preferably 5 to 80%, more preferably 10 to 70% of the repeating unit represented by the formula (1-2) based on the formula (2-2) based on the monomer of the formula (2a) 1 to 90%, preferably 5 to 80%, more preferably 10 to 70% of the repeating unit represented by the formula (M5a) to the formula (M5) based on the monomers of the formulas (M5a) to (M8a).
-2) to 0 to 5 of the repeating unit represented by (M8-2).
0%, preferably 0-40%, more preferably 0-30
%, A repeating unit based on another monomer is 0 to 50%,
Preferably, it can be contained in an amount of 0 to 40%, more preferably 0 to 30%.

The copolymerization reaction for producing the polymer compound of the present invention can be variously exemplified, and is preferably a radical polymerization, an anionic polymerization or a coordination polymerization.

The reaction conditions for the radical polymerization reaction are as follows. An azo compound such as 2,2'-azobisisobutyronitrile or a peroxide such as benzoyl peroxide or lauroyl peroxide is used as an initiator.
(D) The reaction time is 0.5 to 48 hours.
It is preferable to set the time to about the time, but it is not excluded that the time is out of this range.

The reaction conditions for the anionic polymerization reaction are as follows: (a) a hydrocarbon such as benzene, an ether such as tetrahydrofuran, or liquid ammonia as a solvent; (a) a metal such as sodium or potassium as a polymerization initiator; Using an alkyl metal such as -butyllithium or sec-butyllithium, ketyl, or Grignard reagent, (c) maintaining the reaction temperature at about -78 ° C to 0 ° C, and (d) reducing the reaction time from 0.5 hour to 48 hours. It is preferable to use about a time, and (e) a proton-donating compound such as methanol, a halide such as methyl iodide, or another electrophilic substance is preferably used as a terminator, but a case outside this range is not excluded.

The reaction conditions for the coordination polymerization are as follows: (a) using a solvent such as n-heptane and toluene as a solvent;
As a catalyst, a Ziegler-Natta catalyst comprising a transition metal such as titanium and an alkylaluminum, a Phillips catalyst in which chromium and nickel compounds are supported on a metal oxide, an olefin-metathesis mixed catalyst represented by a tungsten and rhenium mixed catalyst, and the like ( C) The reaction temperature is 0 ° C
To about 100 ° C., and (d) the reaction time is preferably about 0.5 to 48 hours, but a case outside this range is not excluded.

The polymer compound of the present invention is effective as a base polymer of a resist material, and the present invention provides a resist material containing the polymer compound, in particular, a chemically amplified positive resist material.

The resist composition of the present invention may contain a compound capable of generating an acid in response to a high energy beam or an electron beam (hereinafter referred to as an acid generator), an organic solvent, and other components as required. .

The acid generator used in the present invention includes: i. An onium salt of the following general formula (P1a-1), (P1a-2) or (P1b); ii. A diazomethane derivative represented by the following general formula (P2), iii. A glyoxime derivative of the following general formula (P3), iv. A bissulfone derivative represented by the following general formula (P4); A sulfonic acid ester of an N-hydroxyimide compound represented by the following general formula (P5), vi. β-ketosulfonic acid derivatives, vii. Disulfone derivatives, viii. A nitrobenzylsulfonate derivative, ix. And sulfonic acid ester derivatives.

[0071]

Embedded image (Wherein, R ^101a , R ^101b , and R ^101c each have 1 to 1 carbon atoms)
12 linear, branched or cyclic alkyl group, alkenyl group, oxoalkyl group or oxoalkenyl group, aryl group having 6 to 20 carbon atoms, or aralkyl group or aryloxoalkyl group having 7 to 12 carbon atoms. A part or all of the hydrogen atoms of these groups may be substituted by an alkoxy group or the like. R ^101b and R ^101c may form a ring, and when forming a ring, R ^101b and R ^101b
101c represents an alkylene group having 1 to 6 carbon atoms. K
^- is a non-nucleophilic counter ion. )

The above-mentioned R ^101a , R ^101b and R ^101c may be the same or different from each other. Specifically, as the alkyl group, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclopropylmethyl group, 4-methylcyclohexyl group, cyclohexylmethyl group, norbornyl group, And adamantyl groups. Examples of the alkenyl group include a vinyl group, an allyl group, a propenyl group, a butenyl group, a hexenyl group, and a cyclohexenyl group. Examples of the oxoalkyl group include a 2-oxocyclopentyl group and a 2-oxocyclohexyl group.
-Oxopropyl group, 2-cyclopentyl-2-oxoethyl group, 2-cyclohexyl-2-oxoethyl group,
A 2- (4-methylcyclohexyl) -2-oxoethyl group and the like can be mentioned. Examples of the aryl group include a phenyl group, a naphthyl group, a p-methoxyphenyl group, m
-Methoxyphenyl group, o-methoxyphenyl group, ethoxyphenyl group, p-tert-butoxyphenyl group,
alkoxyphenyl groups such as m-tert-butoxyphenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, ethylphenyl group, 4-t
alk-naphthyl groups such as tert-butylphenyl group, 4-butylphenyl group and dimethylphenyl group, alkylnaphthyl groups such as methylnaphthyl group and ethylnaphthyl group, methoxynaphthyl group and ethoxynaphthyl group, and dimethylnaphthyl group And dialkylnaphthyl groups such as diethylnaphthyl group, and dialkoxynaphthyl groups such as dimethoxynaphthyl group and diethoxynaphthyl group. Examples of the aralkyl group include a benzyl group, a phenylethyl group, a phenethyl group and the like. Examples of the aryloxoalkyl group include a 2-phenyl-2-oxoethyl group, a 2- (1-naphthyl) -2-oxoethyl group,
And 2-aryl-2-oxoethyl groups such as-(2-naphthyl) -2-oxoethyl group. K ^- a non-nucleophilic counter chloride ions as the ion, halide ions such as bromide ion, triflate, 1,1,1-trifluoroethane sulfonate, fluoroalkyl sulfonate such as nonafluorobutanesulfonate, tosylate, benzenesulfonate , 4-fluorobenzenesulfonate, arylsulfonates such as 1,2,3,4,5-pentafluorobenzenesulfonate, and alkylsulfonates such as mesylate and butanesulfonate.

[0073]

Embedded image (Wherein, R ^102a and R ^102b each represent a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms. R ¹⁰³ represents a linear, branched or cyclic alkylene having 1 to 10 carbon atoms. R ^104a and R ^104b each represent a 2-oxoalkyl group having 3 to 7 carbon atoms. K ⁻ represents a non-nucleophilic counter ion.)

Specific examples of the above R ^102a and R ^102b include methyl, ethyl, propyl, isopropyl, n-
Butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, 4-methylcyclohexyl, cyclohexylmethyl and the like. R ¹⁰³ includes a methylene group,
Ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, 1,4-cyclohexylene, 1,2-cyclohexylene, 1,3-cyclopentene Len group, 1,4-
Examples thereof include a cyclooctylene group and a 1,4-cyclohexanedimethylene group. ^{Examples of} R ^104a and R ^104b include a 2-oxopropyl group, a 2-oxocyclopentyl group, a 2-oxocyclohexyl group, and a 2-oxocycloheptyl group. K ^- is determined by the formulas (P1a-1) and (P1a-
Examples similar to those described in 2) can be given.

[0075]

Embedded image (Wherein, R ¹⁰⁵ and R ¹⁰⁶ represent a linear, branched or cyclic alkyl group or halogenated alkyl group having 1 to 12 carbon atoms, an aryl group or a halogenated aryl group having 6 to 20 carbon atoms,
Or an aralkyl group having 7 to 12 carbon atoms. )

Examples of the alkyl group for R ¹⁰⁵ and R ¹⁰⁶ include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group and an octyl group. Group, amyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, norbornyl group, adamantyl group and the like. Examples of the halogenated alkyl group include a trifluoromethyl group, a 1,1,1-trifluoroethyl group, and a 1,1,1-
Examples thereof include a trichloroethyl group and a nonafluorobutyl group. Examples of the aryl group include an alkoxyphenyl group such as a phenyl group, a p-methoxyphenyl group, an m-methoxyphenyl group, an o-methoxyphenyl group, an ethoxyphenyl group, a p-tert-butoxyphenyl group, and a m-tert-butoxyphenyl group. Examples thereof include an alkylphenyl group such as a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, an ethylphenyl group, a 4-tert-butylphenyl group, a 4-butylphenyl group, and a dimethylphenyl group. Examples of the halogenated aryl group include a fluorophenyl group, a chlorophenyl group, a 1,2,3,4,5-pentafluorophenyl group, and the like. Examples of the aralkyl group include a benzyl group and a phenethyl group.

[0077]

Embedded image (Wherein, R ¹⁰⁷ , R ¹⁰⁸ and R ¹⁰⁹ are a linear, branched or cyclic alkyl group or halogenated alkyl group having 1 to 12 carbon atoms, an aryl group or a halogenated aryl group having 6 to 20 carbon atoms, Or an aralkyl group having 7 to 12 carbon atoms.
^108, R ¹⁰⁹ may form a cyclic structure bonded to each other, indicating when they form a ring, R ^108, R ¹⁰⁹ each represent 1-6 linear, a branched alkylene group. )

Examples of the alkyl group, halogenated alkyl group, aryl group, halogenated aryl group and aralkyl group of R ¹⁰⁷ , R ¹⁰⁸ and R ¹⁰⁹ include the same groups as described for R ¹⁰⁵ and R ¹⁰⁶ . The alkylene group for R ¹⁰⁸ and R ¹⁰⁹ includes a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group and the like.

[0079]

Embedded image (In the formula, R ^101a and R ^101b are the same as described above.)

[0080]

Embedded image (Wherein, R ¹¹⁰ represents an arylene group having 6 to 10 carbon atoms, an alkylene group having 1 to 6 carbon atoms or an alkenylene group having 2 to 6 carbon atoms, and some or all of the hydrogen atoms of these groups further have carbon atoms. It may be substituted by a linear or branched alkyl or alkoxy group, a nitro group, an acetyl group, or a phenyl group having from 1 to 4. R ¹¹¹ has 1 to 8 carbon atoms. Or a substituted alkyl group, alkenyl group or alkoxyalkyl group, phenyl group or naphthyl group, and a part or all of the hydrogen atoms of these groups are further an alkyl group or alkoxy group having 1 to 4 carbon atoms; Or a phenyl group which may be substituted by an alkyl group, an alkoxy group, a nitro group or an acetyl group; a heteroaromatic group having 3 to 5 carbon atoms; or a chlorine atom or a fluorine atom.)

Here, the arylene group for R ¹¹⁰ includes:
1,2-phenylene group, 1,8-naphthylene group and the like, alkylene groups include methylene group, 1,2-ethylene group, 1,3-propylene group, 1,4-butylene group, 1-
Phenyl-1,2-ethylene group, norbornane-2,3
Examples of the -diyl group and the alkenylene group include a 1,2-vinylene group, a 1-phenyl-1,2-vinylene group, and a 5-norbornene-2,3-diyl group. R ^111
Examples of the alkyl group are the same as R ^{101a to} R ^101c, and examples of the alkenyl group include a vinyl group, a 1-propenyl group, an allyl group, a 1-butenyl group, a 3-butenyl group, an isoprenyl group and a 1-pentenyl group. , 3-pentenyl group, 4
-Pentenyl group, dimethylallyl group, 1-hexenyl group, 3-hexenyl group, 5-hexenyl group, 1-heptenyl group, 3-heptenyl group, 6-heptenyl group, 7-octenyl group, etc. , Methoxymethyl group, ethoxymethyl group, propoxymethyl group, butoxymethyl group, pentoxymethyl group, hexyloxymethyl group, heptyloxymethyl group, methoxyethyl group, ethoxyethyl group, propoxyethyl group, butoxyethyl group, pli Roxyethyl, hexyloxyethyl, methoxypropyl, ethoxypropyl, propoxypropyl, butoxypropyl, methoxybutyl, ethoxybutyl, propoxybutyl, methoxypentyl, ethoxypentyl, methoxyhexyl, methoxy Heptyl Etc. The.

It is to be noted that carbon atoms which may be further substituted
Examples of the alkyl group having 4 to 4 include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a tert-butyl group. Group, propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, tert-butoxy group, etc. may be substituted with an alkyl group having 1 to 4 carbon atoms, an alkoxy group, a nitro group or an acetyl group. A phenyl group, a tolyl group, a p-tert-butoxyphenyl group, a p-acetylphenyl group, a p-nitrophenyl group, etc.
Examples of the heteroaromatic group 5 include a pyridyl group and a furyl group.

Specifically, for example, diphenyliodonium trifluoromethanesulfonate, phenyliodonium trifluoromethanesulfonate (p-tert-butoxyphenyl), diphenyliodonium p-toluenesulfonate, p-toluenesulfonic acid (p-tert-
(Butoxyphenyl) phenyliodonium, triphenylsulfonium trifluoromethanesulfonate, trifluoromethanesulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, bis (p-tert-butoxyphenyl) phenylsulfonium trifluoromethanesulfonate, tris trifluoromethanesulfonate (P-tert-butoxyphenyl) sulfonium,
triphenylsulfonium p-toluenesulfonate, p
-(P-tert-butoxyphenyl) diphenylsulfonium toluenesulfonate, bis (p-tert-butoxyphenyl) phenylsulfonium p-toluenesulfonate, tris (p-tert-toluenesulfonate)
(t-butoxyphenyl) sulfonium, triphenylsulfonium nonafluorobutanesulfonate, triphenylsulfonium butanesulfonate, trimethylsulfonium trifluoromethanesulfonate, trimethylsulfonium p-toluenesulfonate, cyclohexylmethyl trifluoromethanesulfonate (2-oxocyclohexyl) Sulfonium, cyclohexylmethyl p-toluenesulfonate (2-oxocyclohexyl) sulfonium, dimethylphenylsulfonium trifluoromethanesulfonate, dimethylphenylsulfonium p-toluenesulfonate, dicyclohexylphenylsulfonium trifluoromethanesulfonate, dicyclohexylphenylsulfonium p-toluenesulfonate , Trifluoromethane sulfone Trinaphthylsulfonium, cyclohexylmethyl trifluoromethanesulfonate (2-oxocyclohexyl) sulfonium, (2-norbonyl) methyl (2-oxocyclohexyl) sulfonium, ethylenebis [methyl (2-oxocyclopentyl) sulfonium trifluoromethanesulfonate Onium salts such as 1,2′-naphthylcarbonylmethyltetrahydrothiophenium triflate, bis (benzenesulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, bis (xylenesulfonyl) diazomethane, bis (cyclohexylsulfonyl) Diazomethane, bis (cyclopentylsulfonyl) diazomethane, bis (n-butylsulfonyl) diazomethane, bis (isobutyl) Ruhoniru)
Diazomethane, bis (sec-butylsulfonyl) diazomethane, bis (n-propylsulfonyl) diazomethane, bis (isopropylsulfonyl) diazomethane, bis (tert-butylsulfonyl) diazomethane, bis (n-amylsulfonyl) diazomethane, bis (isoamylsulfonyl) Diazomethane, bis (sec-amylsulfonyl) diazomethane, bis (tert-amylsulfonyl) diazomethane, 1-cyclohexylsulfonyl-1- (tert-butylsulfonyl) diazomethane, 1-cyclohexylsulfonyl-1- (tert-
Diazomethane derivatives such as amylsulfonyl) diazomethane, 1-tert-amylsulfonyl-1- (tert-butylsulfonyl) diazomethane, bis-O- (p-
Toluenesulfonyl) -α-dimethylglyoxime, bis-O- (p-toluenesulfonyl) -α-diphenylglyoxime, bis-O- (p-toluenesulfonyl)
-Α-dicyclohexylglyoxime, bis-O- (p
-Toluenesulfonyl) -2,3-pentanedione glyoxime, bis-O- (p-toluenesulfonyl) -2
-Methyl-3,4-pentanedione glyoxime, bis-O- (n-butanesulfonyl) -α-dimethylglyoxime, bis-O- (n-butanesulfonyl) -α-diphenylglyoxime, bis-O- (N-butanesulfonyl) -α-dicyclohexylglyoxime, bis-O
-(N-butanesulfonyl) -2,3-pentanedione glyoxime, bis-O- (n-butanesulfonyl)-
2-methyl-3,4-pentanedione glyoxime, bis-O- (methanesulfonyl) -α-dimethylglyoxime, bis-O- (trifluoromethanesulfonyl)-
α-dimethylglyoxime, bis-O- (1,1,1-
Trifluoroethanesulfonyl) -α-dimethylglyoxime, bis-O- (tert-butanesulfonyl)-
α-dimethylglyoxime, bis-O- (perfluorooctanesulfonyl) -α-dimethylglyoxime, bis-O- (cyclohexanesulfonyl) -α-dimethylglyoxime, bis-O- (benzenesulfonyl) -α
-Dimethylglyoxime, bis-O- (p-fluorobenzenesulfonyl) -α-dimethylglyoxime, bis-O- (p-tert-butylbenzenesulfonyl)-
glyoxime derivatives such as α-dimethylglyoxime, bis-O- (xylenesulfonyl) -α-dimethylglyoxime, bis-O- (camphorsulfonyl) -α-dimethylglyoxime, bisnaphthylsulfonylmethane,
Bissulfone derivatives such as bistrifluoromethylsulfonylmethane, bismethylsulfonylmethane, bisethylsulfonylmethane, bispropylsulfonylmethane, bisisopropylsulfonylmethane, bis-p-toluenesulfonylmethane, and bisbenzenesulfonylmethane;
-Cyclohexylcarbonyl-2- (p-toluenesulfonyl) propane, 2-isopropylcarbonyl-2-
Β-ketosulfone derivatives such as (p-toluenesulfonyl) propane; disulfone derivatives such as diphenyldisulfone and dicyclohexyldisulfone; nitro such as 2,6-dinitrobenzyl p-toluenesulfonate and 2,4-dinitrobenzyl p-toluenesulfonate. Benzyl sulfonate derivatives, 1,2,3-tris (methanesulfonyloxy) benzene, 1,2,3-tris (trifluoromethanesulfonyloxy) benzene, 1,2,3-tris (p-toluenesulfonyloxy) benzene and the like Sulfonic acid ester derivatives, N-hydroxysuccinimide methanesulfonic acid ester, N-hydroxysuccinimide trifluoromethanesulfonic acid ester, N-hydroxysuccinimide ethanesulfonic acid ester, N-
Hydroxysuccinimide 1-propanesulfonic acid ester, N-hydroxysuccinimide 2-propanesulfonic acid ester, N-hydroxysuccinimide 1-pentanesulfonic acid ester, N-hydroxysuccinimide 1-octanesulfonic acid ester, N-hydroxysuccinimide p-toluenesulfone Acid ester, N-
Hydroxysuccinimide p-methoxybenzenesulfonate, N-hydroxysuccinimide 2-chloroethanesulfonate, N-hydroxysuccinimidebenzenesulfonate, N-hydroxysuccinimide-2,4,6-trimethylbenzenesulfonate, N-hydroxy Succinimide 1-naphthalenesulfonic acid ester, N-hydroxysuccinimide 2-naphthalenesulfonic acid ester, N-hydroxy-2-phenylsuccinimide methanesulfonic acid ester, N-hydroxymaleimide methanesulfonic acid ester, N-hydroxymaleimidoethanesulfonic acid ester, N-hydroxy-2-phenylmaleimide methanesulfonic acid ester, N-hydroxyglutarimide methanesulfonic acid ester Ether, N- hydroxy glutarimide benzenesulfonate ester, N- hydroxyphthalimide methanesulfonate ester, N- hydroxyphthalimide benzenesulfonate ester, N- hydroxyphthalimide trifluoromethanesulfonate ester,
N-hydroxyphthalimide p-toluenesulfonic acid ester, N-hydroxynaphthalimide methanesulfonic acid ester, N-hydroxynaphthalimidebenzenesulfonic acid ester, N-hydroxy-5-norbornene-2,3-dicarboximide methanesulfonic acid ester N-hydroxy-5-norbornene-2,3-dicarboximide trifluoromethanesulfonic acid ester, N-hydroxy-5-norbornene-2,3-dicarboximide p-toluenesulfonic acid ester, etc.
Sulfonic acid ester derivatives of a hydroxyimide compound, such as triphenylsulfonium trifluoromethanesulfonate, (p-tert-butoxyphenyl) diphenylsulfonium trifluoromethanesulfonate, and tris (pt) trifluoromethanesulfonate;
tert-butoxyphenyl) sulfonium, triphenylsulfonium p-toluenesulfonate, diphenylsulfonium p-toluenesulfonate (p-tert-butoxyphenyl), tris (p-toluenesulfonate)
-Tert-butoxyphenyl) sulfonium, trinaphthylsulfonium trifluoromethanesulfonate, cyclohexylmethyl trifluoromethanesulfonate (2
Onium salts such as -oxocyclohexyl) sulfonium, (2-norbonyl) methyl trifluoromethanesulfonate (2-oxocyclohexyl) sulfonium, 1,2'-naphthylcarbonylmethyltetrahydrothiophenium triflate, bis (benzenesulfonyl) diazomethane, Bis (p-toluenesulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane,
Bis (n-butylsulfonyl) diazomethane, bis (isobutylsulfonyl) diazomethane, bis (sec-butylsulfonyl) diazomethane, bis (n-propylsulfonyl) diazomethane, bis (isopropylsulfonyl) diazomethane, bis (tert-butylsulfonyl) diazomethane, etc. Diazomethane derivative of bis-O-
Glyoxime derivatives such as (p-toluenesulfonyl) -α-dimethylglyoxime, bis-O- (n-butanesulfonyl) -α-dimethylglyoxime, bissulfone derivatives such as bisnaphthylsulfonylmethane, N-hydroxysuccinimide methanesulfonic acid Ester, N-hydroxysuccinimide trifluoromethanesulfonic acid ester, N-hydroxysuccinimide 1-propanesulfonic acid ester, N-hydroxysuccinimide 2
-Propanesulfonic acid ester, N-hydroxysuccinimide 1-pentanesulfonic acid ester, N-hydroxysuccinimide p-toluenesulfonic acid ester,
Sulfonate derivatives of N-hydroxyimide compounds such as N-hydroxynaphthalimide methanesulfonate and N-hydroxynaphthalimidobenzenesulfonate are preferably used. The acid generators may be used alone or in combination of two or more. Onium salts are excellent in the effect of improving rectangularity, and diazomethane derivatives and glyoxime derivatives are excellent in the effect of reducing standing waves. Therefore, fine adjustment of the profile can be performed by combining the two.

The acid generator is preferably added in an amount of 0.1 to 15 parts by weight per 100 parts of the base resin (parts by weight, hereinafter the same).
Parts, more preferably 0.5 to 8 parts. If the amount is less than 0.1 part, the sensitivity may be poor. If the amount is more than 15 parts, the transparency may be reduced and the resolution may be reduced.

The organic solvent used in the present invention may be any organic solvent that can dissolve the base resin, the acid generator, and other additives. Examples of such an organic solvent include ketones such as cyclohexanone and methyl-2-n-amyl ketone, 3-methoxybutanol,
-Methyl-3-methoxybutanol, 1-methoxy-2
Alcohols such as -propanol, 1-ethoxy-2-propanol, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethers such as ethylene glycol monoethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol Monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, propylene glycol monoter
Esters such as t-butyl ether acetate are mentioned, and one of these can be used alone or a mixture of two or more thereof, but is not limited thereto. In the present invention, among these organic solvents, in addition to diethylene glycol dimethyl ether and 1-ethoxy-2-propanol in which the solubility of the acid generator in the resist component is the most excellent, propylene glycol monomethyl ether acetate as a safe solvent and a mixture thereof Solvents are preferably used.

The amount of the organic solvent to be used is preferably 200 to 1,000 parts, more preferably 400 to 800 parts, per 100 parts of the base resin.

In the resist composition of the present invention, a polymer compound different from the polymer compound containing a repeating unit represented by the above formula (1-1) or (1-2) can be added.

As specific examples of the polymer compound, a weight average molecular weight represented by the following formula (R1) and / or (R2) is from 1,000 to 500,000, preferably 5,
000 to 100,000, but are not limited thereto.

[0089]

Embedded image (Wherein, R ⁰⁰¹ is a hydrogen atom, a methyl group or CH ₂ CO ₂ R
⁰⁰³ is shown. R ⁰⁰² is a hydrogen atom, a methyl group or CO ₂ R ⁰⁰³
Is shown. R ⁰⁰³ represents a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms. R ⁰⁰⁴ represents a hydrogen atom or a monovalent hydrocarbon group having a carboxy group or a hydroxyl group having 1 to 15 carbon atoms. At least one of R ^{005 to} R ⁰⁰⁸ represents a carboxy group having 1 to 15 carbon atoms or a monovalent hydrocarbon group containing a hydroxyl group, and the rest are each independently a hydrogen atom or a linear group having 1 to 15 carbon atoms; It represents a branched or cyclic alkyl group. R ^{005 to} R ⁰⁰⁸ may form a ring with each other, in which case at least one of R ^{005 to} R ⁰⁰⁸ is a divalent hydrocarbon group having a carboxy group or a hydroxyl group having 1 to 15 carbon atoms. And the rest each independently represent a single bond or a linear, branched or cyclic alkylene group having 1 to 15 carbon atoms. R ⁰⁰⁹ represents a monovalent hydrocarbon group having a —CO ₂ — partial structure having 3 to 15 carbon atoms. R ⁰¹⁰ to R ⁰¹ at least one ³ -CO ₂ of 2 to 15 carbon atoms - a monovalent hydrocarbon group containing a partial structure, linear hydrogen atom or 1 to 15 carbon atoms in each remaining independently It represents a chain, branched or cyclic alkyl group. R ^{010 to} R ⁰¹³ may form a ring with each other, in which case at least one of R ^{010 to} R ⁰¹³ is a divalent hydrocarbon containing a —CO ₂ — partial structure having 1 to 15 carbon atoms. And the rest each independently represent a single bond or a linear, branched or cyclic alkylene group having 1 to 15 carbon atoms. R ⁰¹⁴ represents a polycyclic hydrocarbon group having 7 to 15 carbon atoms or an alkyl group containing a polycyclic hydrocarbon group. R ⁰¹⁵ represents an acid labile group. R ⁰¹⁶ represents a hydrogen atom or a methyl group. R ⁰¹⁷ represents a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms. X represents CH ₂ or an oxygen atom. k ′ is 0 or 1. a1 ', a2', a
3 ′, b1 ′, b2 ′, b3 ′, c1 ′, c2 ′, c
3 ′, d1 ′, d2 ′, d3 ′, e ′ are numbers of 0 or more and less than 1, and a1 ′ + a2 ′ + a3 ′ + b1 ′ + b2 ′ +
b3 '+ c1' + c2 '+ c3' + d1 '+ d2' + d
3 ′ + e ′ = 1 is satisfied. f ', g', h ', i',
j ′ is a number from 0 to less than 1, and f ′ + g ′ + h ′ +
i ′ + j ′ = 1 is satisfied. In addition, specific examples of each group are the same as those described above.

The compounding ratio of the high molecular compound containing the repeating unit represented by the general formula (1-1) or (1-2) to another high molecular compound is from 100: 0 to 10:90, particularly 100 : 0 to 20:80 by weight. If the blending ratio of the polymer compound containing the repeating unit represented by the above general formula (1-1) or (1-2) is less than this, favorable performance as a resist material may not be obtained. The performance of the resist material can be adjusted by appropriately changing the above mixing ratio.

The polymer compound is not limited to one kind,
More than one species can be added. By using a plurality of types of polymer compounds, the performance of the resist material can be adjusted.

The resist composition of the present invention may further contain a dissolution controlling agent. The dissolution controlling agent has an average molecular weight of 100 to 1,000, preferably 150 to 80.
0 and a compound having two or more phenolic hydroxyl groups in the molecule, wherein the hydrogen atom of the phenolic hydroxyl group is substituted by an acid labile group at an average rate of 0 to 100 mol% or a carboxy group in the molecule. And a compound in which the hydrogen atom of the carboxy group of the compound having the formula (1) is substituted with an acid labile group at an average ratio of 50 to 100 mol% as a whole.

Incidentally, the substitution rate of the hydrogen atom of the phenolic hydroxyl group by the acid labile group is 0 mol% or more, preferably 30 mol% or more of the entire phenolic hydroxyl group on average.
The upper limit is 100 mol%, more preferably 80 mol%. The substitution rate of the hydrogen atom of the carboxy group by the acid labile group is 50 mol% or more, preferably 70 mol% or more of the whole carboxy group on average, and the upper limit is 100 mol%.
It is.

In this case, such a phenolic hydroxyl group is
As the compound having one or more compounds or the compound having a carboxy group, compounds represented by the following formulas (D1) to (D14) are preferable.

[0095]

Embedded image (Wherein, R ²⁰¹ and R ²⁰² each represent a hydrogen atom or a linear or branched alkyl or alkenyl group having 1 to 8 carbon atoms. R ²⁰³ represents a hydrogen atom or a 1 to 8 carbon atom. Represents a linear or branched alkyl or alkenyl group or — (R ²⁰⁷ ) _h COOH, wherein R ²⁰⁴ is — (CH ₂ ) _i
-(I = 2 to 10), an arylene group having 6 to 10 carbon atoms,
It represents a carbonyl group, a sulfonyl group, an oxygen atom or a sulfur atom. R ^{20 5} represents an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, a carbonyl group, a sulfonyl group, an oxygen atom or a sulfur atom. R ²⁰⁶ is a hydrogen atom,
It represents a linear or branched alkyl group or alkenyl group having 1 to 8 carbon atoms, or a phenyl group or a naphthyl group each substituted with a hydroxyl group. R ²⁰⁷ represents a linear or branched alkylene group having 1 to 10 carbon atoms. R ²⁰⁸ represents a hydrogen atom or a hydroxyl group. j is an integer of 0-5. u and h are 0
Or 1. s, t, s ′, t ′, s ″, and t ″ are s + t = 8, s ′ + t ′ = 5, and s ″ + t ″, respectively.
= 4 and has at least one hydroxyl group in each phenyl skeleton. α is the equation (D8),
The number is such that the molecular weight of the compound (D9) is 100 to 1,000. )

In the above formula, R²⁰¹, R²⁰²As, for example, water
Element atom, methyl group, ethyl group, butyl group, propyl group,
Ethynyl group, cyclohexyl group, R²⁰³For example,
R^{Two 01}, R²⁰²The same as above, or -COOH, -C
H_TwoCOOH, R²⁰⁴Are, for example, ethylene group,
Nylene, carbonyl, sulfonyl, oxygen, sulfur
Yellow atom, R²⁰⁵As, for example, a methylene group, or
R²⁰⁴The same as R ²⁰⁶As a hydrogen atom,
Tyl, ethyl, butyl, propyl, ethynyl
Group, cyclohexyl group, and hydroxyl group, respectively.
Phenyl, naphthyl and the like.

As the acid labile group of the dissolution controlling agent, various types can be used, and specifically, the following general formula (L1)
Examples include the group represented by (L4), a tertiary alkyl group having 4 to 20 carbon atoms, a trialkylsilyl group having 1 to 6 carbon atoms in each alkyl group, and an oxoalkyl group having 4 to 20 carbon atoms. it can.

[0098]

Embedded image(Where R^L01, R^L02Is a hydrogen atom or a C1-18
Shows a linear, branched or cyclic alkyl group. R^L03Is
It may have a hetero atom such as an oxygen atom having 1 to 18 carbon atoms.
A monovalent hydrocarbon group. R^L01And R^L02, R^L01And R
^L03, R^L02And R^L03Is bonded to each other to form a ring
When a ring is formed, R^L01, R^L02, R^L03Haso
Linear or branched alkylene having 1 to 18 carbon atoms, respectively
Represents a group. R^{L 04}Is a tertiary alkyl group having 4 to 20 carbon atoms,
Each alkyl group is a trialkyl group having 1 to 6 carbon atoms.
A lyl group, an oxoalkyl group having 4 to 20 carbon atoms or
A group represented by the general formula (L1) is shown. R^L05Has 1 to 1 carbon atoms
Monovalent hydrocarbon groups or carbons which may contain 8 heteroatoms
Represents an optionally substituted aryl group having a prime number of 6 to 20
You. R^L06May contain a heteroatom having 1 to 8 carbon atoms
A monovalent hydrocarbon group or substituted having 6 to 20 carbon atoms
Represents an aryl group. R^L07~ R^L16Are independent
Containing a hydrogen atom or a heteroatom having 1 to 15 carbon atoms
Shows good monovalent hydrocarbon groups. R^L07~ R^L16Are connected to each other
May form a ring, in which case the carbon number is 1
A divalent hydrocarbon group which may contain up to 15 heteroatoms
Show. Also, R ^L07~ R^L16Binds to an adjacent carbon
May be bonded to each other without any intervening to form a double bond.
No. y is an integer of 0-6. m is 0 or 1, n is 0,
1, 2 or 3, 2m + n = 2 or 3
This is the number to be added. Note that specific examples of each group
Are the same as described above.

The blending amount of the above-mentioned dissolution controlling agent depends on the amount of the base resin 1
It is 0 to 50 parts, preferably 0 to 40 parts, more preferably 0 to 30 parts with respect to 00 parts, and can be used alone or in combination of two or more. If the compounding amount exceeds 50 parts, the film of the pattern is reduced, and the resolution may be reduced.

The dissolution controlling agent as described above is used for a compound having a phenolic hydroxyl group or a carboxy group.
It is synthesized by introducing an acid labile group using an organic chemical formulation.

Further, a basic compound can be added to the resist composition of the present invention. As the basic compound, a compound capable of suppressing the diffusion rate when the acid generated from the acid generator diffuses into the resist film is suitable. By compounding a basic compound, the diffusion rate of acid in the resist film is suppressed and the resolution is improved. Etc. can be improved.

Such basic compounds include primary, secondary and tertiary aliphatic amines, hybrid amines,
Aromatic amines, heterocyclic amines, nitrogen-containing compounds having a carboxy group, nitrogen-containing compounds having a sulfonyl group,
Examples include a nitrogen-containing compound having a hydroxyl group, a nitrogen-containing compound having a hydroxyphenyl group, an alcoholic nitrogen-containing compound, an amide derivative, and an imide derivative.

Specifically, the primary aliphatic amines include ammonia, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tertiary aliphatic amines.
t-butylamine, pentylamine, tert-amylamine, cyclopentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine,
Nonylamine, decylamine, dodecylamine, cetylamine, methylenediamine, ethylenediamine, tetraethylenepentamine and the like are exemplified. As secondary aliphatic amines, dimethylamine, diethylamine, di-n
-Propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-sec-butylamine, dipentylamine, dicyclopentylamine,
Dihexylamine, dicyclohexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, didodecylamine, dicetylamine, N, N
-Dimethylmethylenediamine, N, N-dimethylethylenediamine, N, N-dimethyltetraethylenepentamine, and the like. Examples of the tertiary aliphatic amines include trimethylamine, triethylamine, tri-n-propylamine, and triisopropylamine. , Tri-n-butylamine, triisobutylamine, tri-sec-butylamine, tripentylamine, tricyclopentylamine, trihexylamine, tricyclohexylamine,
Triheptylamine, trioctylamine, trinonylamine, tridecylamine, tridodecylamine, tricetylamine, N, N, N ', N'-tetramethylmethylenediamine, N, N, N', N'-tetra Examples include methylethylenediamine, N, N, N ', N'-tetramethyltetraethylenepentamine and the like.

Examples of the mixed amines include dimethylethylamine, methylethylpropylamine, benzylamine, phenethylamine and benzyldimethylamine. Specific examples of aromatic amines and heterocyclic amines include aniline derivatives (for example, aniline,
N-methylaniline, N-ethylaniline, N-propylaniline, N, N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, ethylaniline, propylaniline, trimethylaniline, 2-nitroaniline , 3-nitroaniline, 4-nitroaniline, 2,4-dinitroaniline, 2,6-dinitroaniline, 3,5-dinitroaniline, N, N-
Dimethyl toluidine, etc.), diphenyl (p-tolyl) amine, methyl diphenylamine, triphenylamine,
Phenylenediamine, naphthylamine, diaminonaphthalene, pyrrole derivatives (e.g., pyrrole, 2H-pyrrole, 1-methylpyrrole, 2,4-dimethylpyrrole,
2,5-dimethylpyrrole, N-methylpyrrole, etc.),
Oxazole derivatives (eg, oxazole, isoxazole, etc.), thiazole derivatives (eg, thiazole, isothiazole, etc.), imidazole derivatives (eg, imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, etc.), pyrazole derivatives, furazane derivatives, Pyrroline derivatives (eg, pyrroline, 2-methyl-1-pyrroline, etc.), pyrrolidine derivatives (eg, pyrrolidine, N-methylpyrrolidine, pyrrolidinone, N-methylpyrrolidone, etc.), imidazoline derivatives, imidazolidine derivatives, pyridine derivatives (eg, pyridine, methyl) Pyridine, ethylpyridine, propylpyridine, butylpyridine, 4- (1-butylpentyl) pyridine, dimethylpyridine, trimethylpyridine, triethylpyridine, phenylpyridyl , 3-methyl-2-phenylpyridine, 4-tert-butylpyridine, diphenylpyridine, benzylpyridine, methoxypyridine, butoxypyridine, dimethoxypyridine, 1-methyl-2-pyridone, 4-pyrrolidinopyridine, 1-methyl- 4-phenylpyridine, 2- (1-ethylpropyl) pyridine,
Aminopyridine, dimethylaminopyridine, etc.), pyridazine derivatives, pyrimidine derivatives, pyrazine derivatives, pyrazoline derivatives, pyrazolidine derivatives, piperidine derivatives, piperazine derivatives, morpholine derivatives, indole derivatives, isoindole derivatives, 1H-indazole derivatives, indoline derivatives, quinoline derivatives (Eg, quinoline, 3-quinolinecarbonitrile), isoquinoline derivatives, cinnoline derivatives, quinazoline derivatives, quinoxaline derivatives, phthalazine derivatives, purine derivatives, pteridine derivatives, carbazole derivatives, phenanthridine derivatives, acridine derivatives, phenazine derivatives, 1,1
Examples thereof include 0-phenanthroline derivatives, adenine derivatives, adenosine derivatives, guanine derivatives, guanosine derivatives, uracil derivatives, uridine derivatives and the like.

Further, examples of the nitrogen-containing compound having a carboxy group include aminobenzoic acid, indolecarboxylic acid, and amino acid derivatives (eg, nicotinic acid, alanine, arginine, aspartic acid, glutamic acid, glycine,
Histidine, isoleucine, glycylleucine, leucine, methionine, phenylalanine, threonine, lysine, 3-aminopyrazine-2-carboxylic acid, methoxyalanine), and the like. Examples of pyridinium p-toluenesulfonate include a nitrogen-containing compound having a hydroxyl group, a nitrogen-containing compound having a hydroxyphenyl group, and alcoholic nitrogen-containing compounds such as 2-hydroxypyridine, aminocresol, 2,4-quinolinediol, 3-indole methanol hydrate, monoethanolamine, diethanolamine, triethanolamine, N-ethyldiethanolamine, N, N-diethylethanolamine, triisopropanolamine,
2,2′-iminodiethanol, 2-aminoethanol
3-amino-1-propanol, 4-amino-1-
Butanol, 4- (2-hydroxyethyl) morpholine, 2- (2-hydroxyethyl) pyridine, 1- (2
-Hydroxyethyl) piperazine, 1- [2- (2-hydroxyethoxy) ethyl] piperazine, piperidineethanol, 1- (2-hydroxyethyl) pyrrolidine,
1- (2-hydroxyethyl) -2-pyrrolidinone, 3
-Piperidino-1,2-propanediol, 3-pyrrolidino-1,2-propanediol, 8-hydroxyurolidine, 3-quinuclidinol, 3-tropanol,
Examples thereof include 1-methyl-2-pyrrolidineethanol, 1-aziridineethanol, N- (2-hydroxyethyl) phthalimide, and N- (2-hydroxyethyl) isonicotinamide. Examples of amide derivatives include formamide, N-methylformamide, N, N-dimethylformamide, acetamido, N-methylacetamido,
Examples include N-dimethylacetamide, propionamide, benzamide and the like. Examples of the imide derivative include phthalimide, succinimide, and maleimide.

Further, one or more selected from basic compounds represented by the following general formula (B1) may be blended.

[0107]

Embedded image (In the formula, n = 1, 2, or 3. Each Y independently represents a hydrogen atom or a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms, and may include a hydroxyl group or an ether structure. X each independently represents a group represented by the following general formulas (X1) to (X3), and two or three Xs may combine to form a ring)

[0108]

Embedded image (Wherein, R ³⁰⁰ , R ³⁰² , and R ³⁰⁵ represent a linear or branched alkylene group having 1 to 4 carbon atoms. R ³⁰¹ and R ³⁰⁴ represent a hydrogen atom or a linear alkyl group having 1 to 20 carbon atoms; R ³⁰³ represents a branched or cyclic alkyl group, and may contain one or more hydroxy groups, ether structures, ester structures, or lactone rings, and R ³⁰³ is a single bond or a linear or branched group having 1 to 4 carbon atoms. Represents an alkylene group in the form of

Specific examples of the basic compound represented by the general formula (B1) include tris (2-methoxymethoxyethyl) amine and tris {2- (2-methoxyethoxy) amine.
Ethylamine, tris {2- (2-methoxyethoxymethoxy) ethyl} amine, tris {2- (1-methoxyethoxy) ethyl} amine, tris {2- (1-ethoxyethoxy) ethyl} amine, tris2 -(1-ethoxypropoxy) ethyl} amine, tris [2- {2
-(2-hydroxyethoxy) ethoxydiethyl] amine, 4,7,13,16,21,24-hexaoxa-
1,10-diazabicyclo [8.8.8] hexacosan, 4,7,13,18-tetraoxa-1,10-diazabicyclo [8.5.5] eicosan, 1,4,1
0,13-tetraoxa-7,16-diazabicyclooctadecane, 1-aza-12-crown-4, 1-aza-15-crown-5, 1-aza-18-crown-
6, tris (2-formyloxyethyl) amine, tris (2-formyloxyethyl) amine, tris (2
-Acetoxyethyl) amine, tris (2-propionyloxyethyl) amine, tris (2-butyryloxyethyl) amine, tris (2-isobutyryloxyethyl) amine, tris (2-valeryloxyethyl) amine, Tris (2-pivaloyloxyxyethyl) amine, N, N-bis (2-acetoxyethyl) 2- (acetoxyacetoxy) ethylamine, tris (2-methoxycarbonyloxyethyl) amine, tris (2-te
rt-butoxycarbonyloxyethyl) amine, tris [2- (2-oxopropoxy) ethyl] amine, tris [2- (methoxycarbonylmethyl) oxyethyl] amine, tris [2- (tert-butoxycarbonylmethyloxy) ethyl] Amine, tris [2- (cyclohexyloxycarbonylmethyloxy) ethyl]
Amine, tris (2-methoxycarbonylethyl) amine, tris (2-ethoxycarbonylethyl) amine,
N, N-bis (2-hydroxyethyl) 2- (methoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (methoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2 -(Ethoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (ethoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2- (2
-Methoxyethoxycarbonyl) ethylamine, N, N
-Bis (2-acetoxyethyl) 2- (2-methoxyethoxycarbonyl) ethylamine, N, N-bis (2-
(Hydroxyethyl) 2- (2-hydroxyethoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (2-acetoxyethoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2
-[(Methoxycarbonyl) methoxycarbonyl] ethylamine, N, N-bis (2-acetoxyethyl) 2-
[(Methoxycarbonyl) methoxycarbonyl] ethylamine, N, N-bis (2-hydroxyethyl) 2-
(2-oxopropoxycarbonyl) ethylamine,
N, N-bis (2-acetoxyethyl) 2- (2-oxopropoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2- (tetrahydrofurfuryloxycarbonyl) ethylamine, N, N-bis ( 2
-Acetoxyethyl) 2- (tetrahydrofurfuryloxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2-[(2-oxotetrahydrofuran-3-yl) oxycarbonyl] ethylamine, N,
N-bis (2-acetoxyethyl) 2-[(2-oxotetrahydrofuran-3-yl) oxycarbonyl] ethylamine, N, N-bis (2-hydroxyethyl) 2
-(4-hydroxybutoxycarbonyl) ethylamine, N, N-bis (2-formyloxyethyl) 2-
(4-formyloxybutoxycarbonyl) ethylamine, N, N-bis (2-formyloxyethyl) 2-
(2-formyloxyethoxycarbonyl) ethylamine, N, N-bis (2-methoxyethyl) 2- (methoxycarbonyl) ethylamine, N- (2-hydroxyethyl) bis [2- (methoxycarbonyl) ethyl] amine, N -(2-acetoxyethyl) bis [2- (methoxycarbonyl) ethyl] amine, N- (2-hydroxyethyl) bis [2- (ethoxycarbonyl) ethyl] amine, N- (2-acetoxyethyl) bis [2 -(Ethoxycarbonyl) ethyl] amine, N- (3-hydroxy-1-propyl) bis [2- (methoxycarbonyl)
Ethyl] amine, N- (3-acetoxy-1-propyl) bis [2- (methoxycarbonyl) ethyl] amine, N- (2-methoxyethyl) bis [2- (methoxycarbonyl) ethyl] amine, N-butylbis [2-
(Methoxycarbonyl) ethyl] amine, N-butylbis [2- (2-methoxyethoxycarbonyl) ethyl]
Amine, N-methylbis (2-acetoxyethyl) amine, N-ethylbis (2-acetoxyethyl) amine,
N-methylbis (2-pivaloyloxyxyethyl) amine, N-ethylbis [2- (methoxycarbonyloxy) ethyl] amine, N-ethylbis [2- (tert
-Butoxycarbonyloxy) ethyl] amine, tris (methoxycarbonylmethyl) amine, tris (ethoxycarbonylmethyl) amine, N-butylbis (methoxycarbonylmethyl) amine, N-hexylbis (methoxycarbonylmethyl) amine, β- (diethylamino) -Δ-valerolactone and the like.

Further, one or more kinds of basic compounds having a cyclic structure represented by the following formula (B2) may be blended.

[0111]

Embedded image (Wherein X is the same as above. R ³⁰⁷ has 2 to 2 carbon atoms)
0 is a linear or branched alkylene group, and may contain one or more carbonyl groups, ether structures, ester structures or sulfide structures. )

Specific examples of the basic compound having a cyclic structure represented by the general formula (B2) include 1- [2- (methoxymethoxy) ethyl] pyrrolidine and 1- [2- (methoxymethoxy) ethyl] piperidine. , 4- [2- (methoxymethoxy) ethyl] morpholine, 1- [2-
[(2-methoxyethoxy) methoxy] ethyl] pyrrolidine, 1- [2-[(2-methoxyethoxy) methoxy] ethyl] piperidine, 4- [2-[(2-methoxyethoxy) methoxy] ethyl] morpholine, acetic acid 2-
(1-pyrrolidinyl) ethyl, 2-piperidinoethyl acetate, 2-morpholinoethyl acetate, 2- (1-pyrrolidinyl) ethyl formate, 2-piperidinoethyl propionate,
2-morpholinoethyl acetoxyacetate, methoxyacetic acid 2
-(1-pyrrolidinyl) ethyl, 4- [2- (methoxycarbonyloxy) ethyl] morpholine, 1- [2-
(T-butoxycarbonyloxy) ethyl] piperidine, 4- [2- (2-methoxyethoxycarbonyloxy) ethyl] morpholine, methyl 3- (1-pyrrolidinyl) propionate, methyl 3-piperidinopropionate, 3- Methyl morpholinopropionate, methyl 3- (thiomorpholino) propionate, 2-methyl-3- (1
Methyl-pyrrolidinyl) propionate, ethyl 3-morpholinopropionate, methoxycarbonylmethyl 3-piperidinopropionate, 2-hydroxyethyl 3- (1-pyrrolidinyl) propionate, 2-acetoxyethyl 3-morpholinopropionate, 3 -(1-Pyrrolidinyl) propionic acid 2-oxotetrahydrofuran-3-
Yl, tetrahydrofurfuryl 3-morpholinopropionate, glycidyl 3-piperidinopropionate, 2-methoxyethyl 3-morpholinopropionate, 3- (1-
2- (2-methoxyethoxy) ethyl pyrrolidinyl) propionate, butyl 3-morpholinopropionate, 3-
Cyclohexyl piperidinopropionate, α- (1-pyrrolidinyl) methyl-γ-butyrolactone, β-piperidino-γ-butyrolactone, β-morpholino-δ-valerolactone, methyl 1-pyrrolidinyl acetate, methyl piperidinoacetate, methyl morpholinoacetate And methyl thiomorpholinoacetate, ethyl 1-pyrrolidinyl acetate, 2-methoxyethyl morpholinoacetate, and the like.

Furthermore, one or more selected from basic compounds having a cyano group represented by the following general formulas (B3) to (B6) may be blended.

[0114]

Embedded image (Wherein X, R ³⁰⁷ and n are the same as above. R ³⁰⁸ and R
^{Reference numerals 309} each independently represent a linear or branched alkylene group having 1 to 4 carbon atoms. Examples of the basic compounds having a cyano group represented by the general formulas (B3) to (B6) include 3- (diethylamino) propiononitrile, N, N-bis (2-hydroxyethyl) -3- Aminopropiononitrile, N, N
-Bis (2-acetoxyethyl) -3-aminopropiononitrile, N, N-bis (2-formyloxyethyl) -3-aminopropiononitrile, N, N-bis (2-methoxyethyl) -3- Aminopropiononitrile, N, N-bis [2- (methoxymethoxy) ethyl]
-3-Aminopropiononitrile, methyl N- (2-cyanoethyl) -N- (2-methoxyethyl) -3-aminopropionate, N- (2-cyanoethyl) -N- (2
Methyl-hydroxyethyl) -3-aminopropionate, methyl N- (2-acetoxyethyl) -N- (2-cyanoethyl) -3-aminopropionate, N- (2-
(Cyanoethyl) -N-ethyl-3-aminopropiononitrile, N- (2-cyanoethyl) -N- (2-hydroxyethyl) -3-aminopropiononitrile, N-
(2-acetoxyethyl) -N- (2-cyanoethyl)
-3-Aminopropiononitrile, N- (2-cyanoethyl) -N- (2-formyloxyethyl) -3-aminopropiononitrile, N- (2-cyanoethyl) -N
-(2-methoxyethyl) -3-aminopropiononitrile, N- (2-cyanoethyl) -N- [2- (methoxymethoxy) ethyl] -3-aminopropiononitrile, N- (2-cyanoethyl)- N- (3-hydroxy-1-propyl) -3-aminopropiononitrile, N
-(3-acetoxy-1-propyl) -N- (2-cyanoethyl) -3-aminopropiononitrile, N- (2
-Cyanoethyl) -N- (3-formyloxy-1-propyl) -3-aminopropiononitrile, N- (2-
(Cyanoethyl) -N-tetrahydrofurfuryl-3-aminopropiononitrile, N, N-bis (2-cyanoethyl) -3-aminopropiononitrile, diethylaminoacetonitrile, N, N-bis (2-hydroxyethyl) aminoacetonitrile , N, N-bis (2-acetoxyethyl) aminoacetonitrile, N, N-bis (2
-Formyloxyethyl) aminoacetonitrile, N,
N-bis (2-methoxyethyl) aminoacetonitrile, N, N-bis [2- (methoxymethoxy) ethyl]
Aminoacetonitrile, N-cyanomethyl-N- (2-
Methoxyethyl) -3-aminopropionate methyl, N
-Cyanomethyl-N- (2-hydroxyethyl) -3-
Methyl aminopropionate, N- (2-acetoxyethyl) -N-cyanomethyl-3-methylaminopropionate, N-cyanomethyl-N- (2-hydroxyethyl)
Aminoacetonitrile, N- (2-acetoxyethyl)
-N- (cyanomethyl) aminoacetonitrile, N-cyanomethyl-N- (2-formyloxyethyl) aminoacetonitrile, N-cyanomethyl-N- (2-methoxyethyl) aminoacetonitrile, N-cyanomethyl-
N- [2- (methoxymethoxy) ethyl] aminoacetonitrile, N- (cyanomethyl) -N- (3-hydroxy-1-propyl) aminoacetonitrile, N- (3-
Acetoxy-1-propyl) -N- (cyanomethyl) aminoacetonitrile, N-cyanomethyl-N- (3-formyloxy-1-propyl) aminoacetonitrile,
N, N-bis (cyanomethyl) aminoacetonitrile,
1-pyrrolidinepropiononitrile, 1-piperidinepropiononitrile, 4-morpholinepropiononitrile, 1-pyrrolidineacetonitrile, 1-piperidineacetonitrile, 4-morpholineacetonitrile, cyanomethyl 3-diethylaminopropionate, N, N-bis (2 -Hydroxyethyl) -3-cyanomethyl 3-aminopropionate, N, N-bis (2-acetoxyethyl)-
Cyanomethyl 3-aminopropionate, N, N-bis (2-formyloxyethyl) -3-cyanomethyl 3-aminopropionate, N, N-bis (2-methoxyethyl)
Cyanomethyl-3-aminopropionate, cyanomethyl N, N-bis [2- (methoxymethoxy) ethyl] -3-aminopropionate, 2-cyanoethyl 3-diethylaminopropionate, N, N-bis (2-hydroxy Ethyl) -3-aminopropionic acid (2-cyanoethyl), N, N-bis (2-acetoxyethyl) -3-aminopropionic acid (2-cyanoethyl), N, N-bis (2-formyloxyethyl)- 3-aminopropionic acid (2-cyanoethyl), N, N-bis (2-methoxyethyl) -3-aminopropionic acid (2-cyanoethyl), N, N-bis [2- (methoxymethoxy) ethyl] -3 -Aminopropionic acid (2-cyanoethyl),
Cyanomethyl 1-pyrrolidinepropionate, cyanomethyl 1-piperidinepropionate, cyanomethyl 4-morpholinepropionate, 1-pyrrolidinepropionate (2
-Cyanoethyl), 1-piperidinepropionic acid (2-
Cyanoethyl), 4-morpholinepropionic acid (2-cyanoethyl) and the like.

The compounding amount of the above-mentioned basic compound is based on the amount of the acid generator 1
0.001 to 10 parts, preferably 0.01 to 10 parts by weight
One copy. If the amount is less than 0.001 part, the effect as an additive may not be sufficiently obtained, and if it exceeds 10 parts, the resolution and sensitivity may be reduced.

Further, a compound having a group represented by ≡C-COOH in the molecule can be blended with the resist composition of the present invention.

As the compound having a group represented by ≡C-COOH in the molecule, for example, one or more compounds selected from the following groups I and II can be used, but are not limited thereto. Not something. By blending this component, the PED stability of the resist is improved, and the edge roughness on the nitride film substrate is improved. [Group I] Part or all of the hydrogen atoms of the phenolic hydroxyl group of the compounds represented by the following general formulas (A1) to (A10) is -R ⁴⁰¹ -COOH (R ⁴⁰¹ is a linear or And the molar ratio of the phenolic hydroxyl group (C) to the group (D) represented by ≡C-COOH in the molecule is C / (C + D) = 0.1.
-1.0. [Group II] Compounds represented by the following general formulas (A11) to (A15).

[0118]

Embedded image (Wherein, R ⁴⁰⁸ represents a hydrogen atom or a methyl group. R
⁴⁰² and R ⁴⁰³ each represent a hydrogen atom or a linear or branched alkyl or alkenyl group having 1 to 8 carbon atoms. R
⁴⁰⁴ is a hydrogen atom, a linear or branched alkyl or alkenyl group having 1 to 8 carbon atoms, or-(R ⁴⁰⁹ ) _h -C
OOR 'group (R' is a hydrogen atom or -R ⁴⁰⁹ -COOH)
Is shown. R ⁴⁰⁵ represents — (CH ₂ ) _i — (i = 2 to 10), an arylene group having 6 to 10 carbon atoms, a carbonyl group, a sulfonyl group, an oxygen atom or a sulfur atom. R ⁴⁰⁶ has 1 carbon atom
Represents an alkylene group having 10 to 10, an arylene group having 6 to 10 carbon atoms, a carbonyl group, a sulfonyl group, an oxygen atom or a sulfur atom. R ⁴⁰⁷ represents a hydrogen atom, a linear or branched alkyl group or alkenyl group having 1 to 8 carbon atoms, a phenyl group or a naphthyl group each substituted with a hydroxyl group. R
⁴⁰⁹ represents a linear or branched alkylene group having 1 to 10 carbon atoms. R ⁴¹⁰ represents a hydrogen atom, a linear or branched alkyl group or alkenyl group having 1 to 8 carbon atoms, or —R ^411.
-COOH group is shown. R ⁴¹¹ represents a linear or branched alkylene group having 1 to 10 carbon atoms. j is an integer of 0-5. u and h are 0 or 1. s1, t1, s2, t
2, s3, t3, s4, and t4 are s1 + t1 =
8, s2 + t2 = 5, s3 + t3 = 4, s4 + t4 = 6
And at least one hydroxyl group in each phenyl skeleton. κ is a number that makes the compound of the formula (A6) have a weight average molecular weight of 1,000 to 5,000. λ represents the compound of the formula (A7) having a weight average molecular weight of 1,000.
This is a number from 0 to 10,000. )

[0119]

Embedded image ( ^R402 , ^R403 , and ^R411 have the same meaning as described above.
⁴¹² represents a hydrogen atom or a hydroxyl group. s5 and t5 are s5
≧ 0 and t5 ≧ 0, which are numbers that satisfy s5 + t5 = 5. h ′ is 0 or 1. )

As this component, specifically, the following general formula AI
Compounds represented by -1 to 14 and AII-1 to 10 can be exemplified, but are not limited thereto.

[0121]

Embedded image (R '' represents a hydrogen atom or CH ₂ COOH radical, R "in each compound from 10 to 100 mol% 'of CH ₂ CO
OH group. α and κ have the same meanings as described above. )

[0122]

Embedded image

The compounds having a group represented by ≡C—COOH in the molecule can be used alone or in combination of two or more.

The amount of the compound having a group represented by ≡C-COOH in the molecule is 0 to 5 parts, preferably 0.1 to 5 parts, more preferably 0.1 to 5 parts, based on 100 parts of the base resin. To 3 parts, more preferably 0.1 to 2 parts. 5
If the number is more than the number, the resolution of the resist material may be reduced.

Further, an acetylene alcohol derivative can be added to the resist composition of the present invention as an additive, whereby the storage stability can be improved.

As the acetylene alcohol derivative, those represented by the following formulas (S1) and (S2) can be suitably used.

[0127]

Embedded image (Wherein, R ⁵⁰¹ , R ⁵⁰² , R ⁵⁰³ , R ⁵⁰⁴ , and R ⁵⁰⁵ are each a hydrogen atom or a linear, branched, or cyclic alkyl group having 1 to 8 carbon atoms, and X and Y are 0 or Indicates a positive number and satisfies the following values: 0 ≦ X ≦ 30, 0 ≦ Y ≦ 30, 0 ≦ X
+ Y ≦ 40. )

As acetylene alcohol derivatives, Surfynol 61, Surfynol 82, Surfynol 104, Surfynol 104E, Surfynol 104H, Surfynol 104A, Surfynol TG, Surfynol PC, Surfynol 44 are preferred.
0, Surfynol 465, Surfynol 485 (A
ir Products and Chemicals
Inc. And Surfynol E1004 (manufactured by Nissin Chemical Industry Co., Ltd.).

The acetylene alcohol derivative is added in an amount of 0.01 to 2% by weight, more preferably 0.02 to 1% by weight, based on 100% by weight of the resist composition. 0.0
If the amount is less than 1% by weight, the effect of improving coating properties and storage stability may not be sufficiently obtained.

The resist composition of the present invention may contain, as an optional component, other than the above components, a surfactant which is commonly used to improve coating properties. In addition, the addition amount of the optional component can be a normal amount as long as the effect of the present invention is not impaired.

The surfactant is preferably a nonionic surfactant, and is preferably a perfluoroalkylpolyoxyethylene ethanol, a fluorinated alkyl ester, a perfluoroalkylamine oxide, a perfluoroalkylEO adduct, or a fluorine-containing organosiloxane-based surfactant. And the like. For example, Florad “FC-430”, “F
C-431 "(all manufactured by Sumitomo 3M Limited), Surflon" S-141 "," S-145 "(all manufactured by Asahi Glass Co., Ltd.), Unidyne" DS-401 "," DS
-403 "," DS-451 "(all manufactured by Daikin Industries, Ltd.), MegaFac" F-8151 "(manufactured by Dainippon Ink Industries, Ltd.)," X-70-092 "," X-7 "
0-093 "(all manufactured by Shin-Etsu Chemical Co., Ltd.) and the like. Preferably, Florad “FC-4”
30 "(manufactured by Sumitomo 3M Limited)," X-70-09 "
3 "(manufactured by Shin-Etsu Chemical Co., Ltd.).

A pattern can be formed using the resist material of the present invention by a known lithography technique. For example, a film having a thickness of 0 is formed on a substrate such as a silicon wafer by a method such as spin coating. 0.2-2.0μ
m on a hot plate.
１５０150 ° C., 1-10 minutes, preferably 80-130
Pre-bake at ℃ for 1-5 minutes. Next, a mask for forming a target pattern is held over the resist film, and a high energy ray such as far ultraviolet rays, excimer laser, or X-rays or an electron beam is exposed at a dose of about 1 to 200 mJ / cm ² , preferably 5 to 200 mJ / cm ^2. After irradiating to about 100 mJ / cm ² , the temperature is 60 to 150 ° C. on a hot plate.
Post-exposure bake (PEB) for ８０5 minutes, preferably 80-130 ° C. for 1-3 minutes. Furthermore, 0.1
0.1 to 3 minutes, preferably 0.5 to 2 minutes, using a developing solution of an aqueous alkali solution such as 5 to 5%, preferably 2 to 3% tetramethylammonium hydroxide (TMAH).
The target pattern is formed on the substrate by developing by a conventional method such as a dipping method, a paddle method, a spray method or the like. In addition, the material of the present invention is 248 to 193 nm even among high energy rays.
It is most suitable for fine patterning by deep ultraviolet ray or excimer laser, X-ray and electron beam. In addition, when the above range is out of the upper limit and the lower limit, a desired pattern may not be obtained.

[0133]

The resist material using the polymer compound of the present invention as a base resin is sensitive to high-energy rays, and has excellent sensitivity, resolution and etching resistance. Useful. In particular, since the absorption at the exposure wavelength of an ArF excimer laser or a KrF excimer laser is small, a fine pattern perpendicular to the substrate can be easily formed.

[0134]

EXAMPLES The present invention will be specifically described below with reference to Synthesis Examples and Examples, but the present invention is not limited to the following Examples. [Synthesis Example] The polymer compound of the present invention was synthesized according to the following formulation.

[Synthesis Example 1] Synthesis of Polymer 1 35.6 g of 4- (5-norbornen-2-yl) -4
-Butanolide (synthesized from 5-norbornene-2-carbaldehyde in three steps), 78.0 g of 5-norbornene-
2-ethyl-2-norbornyl 2-carboxylate and 4
9.0 g of maleic anhydride was dissolved in 150 ml of tetrahydrofuran, and 1.8 g of 2,2'-azobisisobutyronitrile was added. After stirring at 60 ° C. for 15 hours,
It was concentrated under reduced pressure. The obtained residue was dissolved in 400 ml of tetrahydrofuran and added dropwise to 10 L of n-hexane. The resulting solid was collected by filtration, washed with 10 L of n-hexane, and vacuum-dried at 40 ° C. for 6 hours.
As a result, 77.1 g of a polymer compound represented by the following formula Polymer 1 was obtained. The yield was 47.4%.

[Synthesis Examples 2 to 12] Polymers 2-1
Synthesis of 2 In the same manner as described above or by a known formulation, Polymer
2 to 12 were synthesized.

[0137]

Embedded image

[0138]

Embedded image

[0139]

Embedded image

Example I The polymer compound of the present invention was evaluated for adhesion to a substrate when blended in a resist material as a base resin. [Examples I-1 to 5 and Comparative Examples 1 and 2] Polymers (Polymers 1 to 5) represented by the above formula and polymers represented by the following formulas (Polymer 13, 14) for comparison
Is a base resin, and an acid generator represented by the following formula (PAG)
1), a basic compound and a solvent were mixed in the composition shown in Table 1. Next, they were filtered with a Teflon (registered trademark) filter (pore size: 0.2 μm) to obtain a resist material.

[0141]

Embedded image

[0142]

Embedded image

The resist solution was spin-coated on a silicon wafer sprayed with hexamethyldisilazane at 90 ° C. for 40 seconds, and heat-treated at 110 ° C. for 90 seconds to form a film having a thickness of 0.5
A μm resist film was formed. This was exposed using a KrF excimer laser stepper (manufactured by Nikon Corporation, NA = 0.5), and after a heat treatment at 110 ° C. for 90 seconds,
Paddle development was performed for 60 seconds using a 2.38% aqueous solution of tetramethylammonium hydroxide to form a 1: 1 line and space pattern. The developed wafer was observed with an overhead SEM (scanning electron microscope), and the minimum line width (μm) remaining without peeling was defined as the adhesion limit of the evaluation resist.

Table 1 shows the composition of each resist and the evaluation results. In Table 1, the solvent and the basic compound are as follows. All solvents used contained 0.01% by weight of FC-430 (manufactured by Sumitomo 3M Limited). PGMEA: propylene glycol methyl ether acetate TBA: tributylamine From the results in Table 1, it was confirmed that the polymer compound of the present invention had high substrate adhesion.

Example II The resist composition of the present invention was evaluated for its resolution in KrF excimer laser exposure. [Examples II-1 to 21] Evaluation of resolution of resist Polymers represented by the above formula (Polymers 1 to 12)
Is a base resin, and an acid generator represented by the following formula (PAG)
1, 2), a dissolution controlling agent represented by the following formula (DRR1 to
4), a basic compound, a compound represented by the following formula:
Compound having a group represented by COOH (ACC1, 2)
And the solvent were mixed in the composition shown in Table 1. Next, they were filtered with a Teflon filter (pore size: 0.2 μm) to obtain a resist material.

[0146]

Embedded image

[0147]

Embedded image

[0148]

Embedded image

The resist solution was spin-coated on a silicon wafer sprayed with hexamethyldisilazane at 90 ° C. for 90 seconds, and heat-treated at 110 ° C. for 90 seconds to form a film having a thickness of 0.5
A μm resist film was formed. This was exposed using a KrF excimer laser stepper (manufactured by Nikon Corporation, NA = 0.5), and after a heat treatment at 110 ° C. for 90 seconds,
Paddle development was performed for 60 seconds using a 2.38% aqueous solution of tetramethylammonium hydroxide to form a 1: 1 line and space pattern. The developed wafer is cut and observed with a cross-sectional SEM (scanning electron microscope), and an exposure amount for resolving a 0.30 μm line and space at 1: 1 (optimal exposure amount = Eop, mJ / cm ² ).
The minimum line width (μm) of the separated line and space in was used as the resolution of the evaluation resist.

Table 2 shows the composition of each resist and the evaluation results. In Table 2, the solvent and the basic compound are as follows. All solvents used contained 0.01% by weight of FC-430 (manufactured by Sumitomo 3M Limited). PGMEA: Propylene glycol methyl ether acetate TEA: Triethanolamine TMMEA: Trismethoxymethoxymethoxyethylamine TMMEA: Trismethoxyethoxymethoxyethylamine From the results in Table 2, the resist material of the present invention shows that the resist material of the present invention has high sensitivity and high resolution in KrF excimer laser exposure. Sex was confirmed.

Example III The resist material of the present invention was evaluated for resolution in ArF excimer laser exposure. [Examples III-1 and II] Evaluation of resist resolution In the same manner as described above, resist materials having the compositions shown in Table 3 were prepared.

The resist solution was spin-coated on a silicon wafer sprayed with hexamethyldisilazane at 90 ° C. for 90 seconds, and heat-treated at 110 ° C. for 90 seconds to form a film having a thickness of 0.5
A μm resist film was formed. This was exposed using an ArF excimer laser stepper (manufactured by Nikon Corporation, NA = 0.55), and subjected to a heat treatment at 110 ° C. for 90 seconds.
Paddle development was performed for 60 seconds using a 2.38% aqueous solution of tetramethylammonium hydroxide to form a 1: 1 line and space pattern. The developed wafer is cut and observed with a cross-sectional SEM (scanning electron microscope), and an exposure amount (optimal exposure amount = Eop, mJ / cm ² ) that resolves a 0.25 μm line and space at a ratio of 1: 1.
The minimum line width (μm) of the separated line and space in was used as the resolution of the evaluation resist.

Table 3 shows the composition and evaluation results of each resist. In Table 3, the solvent and the basic compound are as follows. All solvents used contained 0.01% by weight of FC-430 (manufactured by Sumitomo 3M Limited). PGMEA: Propylene glycol methyl ether acetate TEA: Triethanolamine TMMEA: Trismethoxymethoxyethylamine

From the results shown in Table 3, it was confirmed that the resist material of the present invention had high sensitivity and high resolution in ArF excimer laser exposure.

[0155]

[Table 1]

[0156]

[Table 2]

[0157]

[Table 3]

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Seiichiro Tachibana 28-1 Nishifukushima, Oku-ku, Nakakushiro-mura, Niigata Pref. Shin-Etsu Chemical Co., Ltd. 28-1 Nishifukushima, Gunsu-gun Castle Village Shin-Etsu Chemical Co., Ltd.Shin-Etsu Chemical Co., Ltd. (72) Inventor Satoshi Hasegawa 28-1 Nishi-Fukushima, Kutsujo-mura, Nakakubiki-gun, Niigata Shin-Etsu Chemical Co., Ltd. In-house (72) Inventor Takeshi Watanabe 28-1 Nishifukushima, Oaza, Kushiro-mura, Nakakushijo-gun, Niigata Shin-Etsu Chemical Co., Ltd. -1 Shin-Etsu Chemical Co., Ltd. New Functional Materials Technology Research Institute F-term (reference) 2H025 AA01 AA02 AA09 AB16 AC04 AC06 AC08 AD03 BE00 BE10 BG00 CB08 CB10 CB41 CB55 CB56 FA17 4J032 BA07 BB06 BC01 BC03 CA36 CA46 CB01 CB04 CB05 CB12 CD00 CD09 CE03 CG06 4J100 AK32R AL08Q AR09P AR09Q AR11P AR11Q BA05Q BA06Q BA10Q CA11 BC03Q01 BC03 BC03 BC03 BC03 BC01 BC03

Claims (7)

[Claims] 1. A polymer compound having a weight average molecular weight of 1,000 to 500,000, comprising a repeating unit represented by the following general formula (1-1) or (1-2). Embedded image (In the formula, k is 0 or 1. m is 0, 1, 2, 3, or 4. n is 1 or 2.) 2. The polymer compound according to claim 1, further comprising a repeating unit represented by the following general formula (2-1) in addition to the repeating unit represented by the general formula (1-1). . Embedded image (In the formula, k is the same as above. R ¹ represents a hydrogen atom, a methyl group or CH ₂ CO ₂ R ^3. R ² represents a hydrogen atom, a methyl group or CO ₂ R ^3. R ³ is a carbon atom. R ⁴ represents an acid labile group, R ⁵ represents a halogen atom, a hydroxyl group, a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms. Cyclic alkoxy group, acyloxy group, alkylsulfonyloxy group,
Or a linear, branched, or cyclic alkoxyalkoxy group or an alkoxycarbonyloxy group having 2 to 15 carbon atoms, in which part or all of the hydrogen atoms on the constituent carbon atoms may be substituted with halogen atoms. Z is a single bond or a linear, branched or cyclic (p +
2) a valent hydrocarbon group, and when it is a hydrocarbon group, one or more methylene groups may be substituted with an oxygen atom to form a chain or cyclic ether; One hydrogen atom may be replaced by an oxygen atom to form a ketone. p is 0, 1 or 2. ) 3. The method according to claim 1, further comprising a repeating unit represented by the following general formulas (2-1) and (3) in addition to the repeating unit represented by the general formula (1-1).
The polymer compound as described in the above. Embedded image (In the formula, k, p, and R ^{1 to} R ⁵ are the same as described above.) 4. A repeating unit represented by the following general formula (4), a repeating unit represented by the following general formula (2-1), and a repeating unit represented by the following general formula (2-1) in addition to the repeating unit represented by the above general formula (1-1). The polymer compound according to claim 1, comprising a repeating unit represented by (4) and a repeating unit represented by the following general formula (3). Embedded image (In the formula, k, p, and R ^{1 to} R ⁵ are the same as described above.) 5. The polymer compound according to claim 1, further comprising a repeating unit represented by the following general formula (2-2) in addition to the repeating unit represented by the general formula (1-2). . Embedded image (In the formula, k, p, and R ^{1 to} R ⁵ are the same as described above.) 6. A resist material comprising the polymer compound according to claim 1. Description: 7. A step of applying the resist material according to claim 6 on a substrate, a step of exposing with a high energy ray or an electron beam through a photomask after the heat treatment, and a step of subjecting to a heat treatment if necessary. And developing using a developing solution.