JP2003064134A - High molecular compound, resist material and method for forming pattern - Google Patents

Abstract

(57) Abstract: A repeating unit represented by the formula (1) and an adamantane structure or tetracyclo [4.4.0.
^12.5 . 1 ^7,10 ] a repeating unit having a carboxylic acid protected by an acid-decomposable protecting group having a dodecane structure. Embedded image (Wherein, R ¹ represents a hydrogen atom or a methyl group; R ² represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms; R ³ represents a hydrogen atom or CO ₂ R ⁴ ; R ⁴ represents a carbon number) The resist material based on the polymer compound of the present invention is sensitive to high energy rays and has excellent sensitivity, resolution, and etching resistance. Useful for microfabrication with lines and deep UV.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention uses (1) a polymer compound containing a specific repeating unit, (2) a resist material containing this polymer compound as a base resin, and (3) this resist material. The pattern forming method described above.

[0002]

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

In the resist material for KrF excimer laser, polyhydroxystyrene, which has both practical level of transparency and etching resistance, has become the de facto standard base resin. On the other hand, in the resist material for ArF excimer laser, for example, JP-A-9-73173 and JP-A-9-73173 are used.
As described in Japanese Patent Publication No. 90637, etc., a relatively large amount of a polyacrylic acid or polymethacrylic acid derivative containing an adamantane structure in its side chain is used, but it is said that it does not necessarily exhibit sufficient performance. hard.

That is, a resist material containing a polyacrylic acid or polymethacrylic acid derivative as a base resin is exposed to light,
Although it shows good sensitivity and resolution for pattern formation by development, its dry etching resistance is extremely low. It is possible to improve the dry etching resistance to some extent by introducing a large number of polycyclic structures represented by the adamantane structure to increase the carbon density, but at that time, the hydrophobicity of the resin as a whole becomes high and the adhesion of the substrate Not only does it cause undesired phenomena such as pattern peeling due to deterioration, development defects due to repelling of the developer, but solubility in safety solvents such as propylene glycol monomethyl ether acetate becomes extremely poor, making it impractical. . While further miniaturization of pattern rules is required, in addition to exhibiting excellent performance in sensitivity and resolution, it has excellent substrate adhesion and developer affinity while having practically sufficient etching resistance. Furthermore, there is a need for a base resin for resist materials that has high solubility in solvents.

[0005]

The present invention has been made in view of the above circumstances. (1) It has a high resolution and a practical level of etching resistance, is excellent in substrate adhesion and developer affinity, and is propylene. A polymer compound for a resist material, which has high solubility in a glycol solvent such as glycol monomethyl ether acetate, (2) a resist material containing the polymer compound as a base resin, and (3) a pattern forming method using the resist material. The purpose is to provide.

[0006]

Means for Solving the Problems and Modes for Carrying Out the Invention As a result of extensive studies conducted by the present inventor to achieve the above object, a repeating unit represented by the following general formula (1) obtained by the method described below was obtained. , Adamantane structure or tetracyclo [4.4.0.1 ^2,5 . A polymer compound having a weight average molecular weight of 1,000 to 500,000, which comprises a repeating unit having a carboxylic acid protected by an acid-decomposable protecting group containing a ^1,7,10 ] dodecane structure, is used for a resist material. It is useful as a resin, and a resist material that uses this polymer compound as a base resin has high resolution and practical level of etching resistance, and also has the necessary properties such as substrate adhesion, developer affinity, and solvent solubility. It was also found that this resist material is also excellent, and that this resist material is extremely effective for precise microfabrication.

That is, the present invention provides the following polymer compounds. [I] The repeating unit represented by the following general formula (1) and an adamantane structure or tetracyclo [4.4.0.
1 ^2,5 . And a repeating unit having a carboxylic acid protected by an acid-decomposable protecting group containing a ^1,7,10 ] dodecane structure.
10,000 high molecular compounds.

[Chemical 3] (In the formula, R ¹ represents a hydrogen atom or a methyl group. R ² represents a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms. R ³ represents a hydrogen atom or CO ₂ R. ⁴ shows the .R ⁴
Represents a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms. ) [II] adamantane structure or tetracyclo [4.4.
0.1 ^2,5 . The repeating unit having a carboxylic acid protected by an acid-decomposable protecting group containing a ^1,7,10 ] dodecane structure is any one or more of the units represented by the following general formulas (2) to (4). The polymer compound according to [I].

[Chemical 4] (In the formula, R ⁵ , R ⁷ , and R ¹⁰ represent a hydrogen atom or a methyl group. R ⁶ , R ⁸ , R ⁹ , and R ¹¹ are linear groups having 1 to 15 carbon atoms,
A branched or cyclic alkyl group is shown. ) Further, the present invention provides the following resist materials. [III] A resist material comprising the polymer compound according to [I] or [II]. Furthermore, the present invention provides the following pattern forming method. [IV] A step of applying the resist material described in [III] on a substrate, a step of exposing with a high energy beam or an electron beam through a photomask after heat treatment, and after heat treatment as needed, development. And a step of developing using a liquid.

As described above, generally, polyacrylic acid or polymethacrylic acid derivative has extremely low dry etching resistance, and in order to compensate for the drawback, an adamantane structure or tetracyclo [4.4.0.1 ^2,5 . It is necessary to introduce a considerable amount of units containing a ^1,7,10 ] dodecane structure, but in that case the hydrophobicity as a whole becomes high, and the substrate adhesion, developer affinity, and solvent solubility decrease. . On the other hand, the repeating unit represented by the general formula (1) has an extremely high hydrophilicity, but the adamantane structure and tetracyclo [4.4.0.1 ^2,5 . When combined with a unit containing a [ ^17,10 ] dodecane structure, a suitable developer affinity and solvent solubility can be exhibited. In addition, the above general formula (1)
Since the oxygen functional group is efficiently arranged in the cyclic unit, the decrease in dry etching resistance due to the decrease in carbon density is minimized. Therefore, a resist material using this polymer compound as a base resin has excellent performance in sensitivity and resolution, has a practical level of dry etching resistance, and has substrate adhesion, developer affinity, and solvent solubility. It is extremely useful for forming a fine pattern, which is excellent in various characteristics such as.

The present invention will be described in more detail below.
The novel polymer compound of the present invention comprises a repeating unit represented by the following general formula (1), an adamantane structure or tetracyclo [4.4.0.1 ^2,5 . And a repeating unit having a carboxylic acid protected by an acid-decomposable protecting group containing a ^1,7,10 ] dodecane structure.

[0010]

[Chemical 5]

Here, R ¹ represents a hydrogen atom or a methyl group. R ² represents a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group,
sec-butyl group, tert-butyl group, tert-amyl group, n-pentyl group, n-hexyl group, cyclopentyl group, cyclohexyl group, cyclopentylmethyl group,
Examples thereof include a cyclopentylethyl group, a cyclohexylmethyl group and a cyclohexylethyl group. R ³ represents a hydrogen atom or CO ₂ R ⁴ . R ⁴ is a straight chain having 1 to 15 carbon atoms,
Indicates a branched or cyclic alkyl group, specifically, 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 ter.
Examples include t-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 group and the like. it can.

In the polymer compound of the present invention, the adamantane structure or tetracyclo [4.4.0.
1 ^2,5 . The repeating unit having a carboxylic acid protected by an acid-decomposable protecting group containing a ^1,7,10 ] dodecane structure is
Any one of the units represented by the following general formulas (2) to (4)
More than one species is preferred.

[0013]

[Chemical 6]

Here, R ⁵ , R ⁷ and R ¹⁰ represent a hydrogen atom or a methyl group. R ⁶ , R ⁸ , R ⁹ , and R ^{11 have 1} to 15 carbon atoms
Is a linear, branched or cyclic alkyl group, and specific examples thereof are the same as those listed for R ⁴ .

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

[0016]

[Chemical 7]

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

[0018]

[Chemical 8]

Specific examples of the repeating unit represented by the general formula (3) are shown below, but the invention is not limited thereto.

[0020]

[Chemical 9]

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

[0022]

[Chemical 10]

The polymer compound of the present invention may further contain, if necessary, one or more selected from the repeating units represented by the following general formulas (M1) to (M9).

[0024]

[Chemical 11] (In the formula, R ⁰⁰¹ is a hydrogen atom, a methyl group or CH ₂ CO ₂ R
Indicates ⁰⁰³ . R ⁰⁰² is a hydrogen atom, a methyl group or CO ₂ R ⁰⁰³
Indicates. R ⁰⁰³ represents a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms. R ⁰⁰⁴ represents a hydrogen atom, a carboxy group having 1 to 15 carbon atoms, or a monovalent hydrocarbon group containing a hydroxyl group. At least one of R ^{005 to} R ^{008 represents} a monovalent hydrocarbon group having a carboxy group having 1 to 15 carbon atoms or a hydroxyl group, and the rest independently represent a hydrogen atom or a straight chain having 1 to 15 carbon atoms, A branched or cyclic alkyl group is shown. R ^{005 to} R ⁰⁰⁸ may combine with each other to form a ring, in which case at least one of R ^{005 to} R ⁰⁰⁸ is a divalent carbon atom containing a carboxy group or a hydroxyl group having 1 to 15 carbon atoms. A hydrogen group is shown, and the rest are each independently a single bond or a linear, branched or cyclic alkylene group having 1 to 15 carbon atoms. R ⁰⁰⁹ represents a monovalent hydrocarbon group containing a —CO ₂ — partial structure having 3 to 15 carbon atoms. R ^{0 10 to} R ⁰¹³
At least 1 represents a monovalent hydrocarbon group containing a —CO ₂ — partial structure having 2 to 15 carbon atoms, and the rest each independently represents a hydrogen atom or a straight chain, branched or 1 to 15 carbon atom. A cyclic alkyl group is shown. R ⁰¹⁰ to R ⁰¹³ may be bonded to each other to form a ring, in which case R ⁰¹⁰ to R
^At least one of ^C 13 s represents a divalent hydrocarbon group containing a —CO ₂ — partial structure having 1 to 15 carbon atoms, and the rest are each independently a single bond or a linear or branched C 1 to 15 carbon atom. Alternatively, it represents a cyclic alkylene group. R ⁰¹⁴ has 7 to 15 carbon atoms
Represents a polycyclic hydrocarbon group or an alkyl group containing a polycyclic hydrocarbon group. R ⁰¹⁵ represents an acid labile group. X is CH ₂
Or represents an oxygen atom. Y is -O- ^or- (NR ⁰¹⁶ )-
R ⁰¹⁶ represents a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms. k is 0 or 1
Is. )

Here, R ⁰⁰¹ represents a hydrogen atom, a methyl group or CH ₂ CO ₂ R ⁰⁰³ . A specific example of R ⁰⁰³ 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 cyclohexyl group, ethylcyclopentyl group, butylcyclopentyl group, ethylcyclohexyl group, butylcyclohexyl group, adamantyl group, ethyladamantyl group and butyladamantyl group. R ⁰⁰⁴ represents a hydrogen atom or a monovalent hydrocarbon group containing a carboxy group having 1 to 15 carbon atoms or a hydroxyl group, and specifically, a hydrogen atom, carboxyethyl, carboxybutyl, carboxycyclopentyl, carboxycyclohexyl, carboxynorborne. Examples thereof include nyl, carboxyadamantyl, hydroxyethyl, hydroxybutyl, hydroxycyclopentyl, hydroxycyclohexyl, hydroxynorbornyl, hydroxyadamantyl and the like. R ⁰⁰⁵ ~
At least one of R ^{008 represents} a monovalent hydrocarbon group containing a carboxy group having 1 to 15 carbon atoms or a hydroxyl group, and the rest are each independently a hydrogen atom or a linear, branched or C 1 to 15 carbon atom. A cyclic alkyl group is shown. 1 to 1 carbon atoms
As the monovalent hydrocarbon group having a carboxy group or a hydroxyl group of 5, specifically, carboxy, carboxymethyl, carboxyethyl, carboxybutyl, hydroxymethyl, hydroxyethyl, hydroxybutyl, 2-carboxyethoxycarbonyl, 4- Carboxybutoxycarbonyl, 2-hydroxyethoxycarbonyl, 4-
Examples include hydroxybutoxycarbonyl, carboxycyclopentyloxycarbonyl, carboxycyclohexyloxycarbonyl, carboxynorbornyloxycarbonyl, carboxyadamantyloxycarbonyl, hydroxycyclopentyloxycarbonyl, hydroxycyclohexyloxycarbonyl, hydroxynorbornyloxycarbonyl, and hydroxyadamantyloxycarbonyl. it can. Specific examples of the linear, branched, or cyclic alkyl group having 1 to 15 carbon atoms are the same as those exemplified for R ⁰⁰³ . R ^{005 to} R ⁰⁰⁸ may combine with each other to form a ring, in which case at least one of R ^{005 to} R ⁰⁰⁸ is a divalent carbon atom containing a carboxy group or a hydroxyl group having 1 to 15 carbon atoms. A hydrogen group is shown, and the rest are each independently a single bond or a linear, branched or cyclic alkylene group having 1 to 15 carbon atoms. As the divalent hydrocarbon group having a carboxy group or a hydroxyl group having 1 to 15 carbon atoms, one hydrogen atom is specifically selected from those exemplified as the monovalent hydrocarbon group having a carboxy group or a hydroxyl group. The removed one can be exemplified. 1 to 1 carbon atoms
Specific examples of the linear, branched, or cyclic alkylene group of 5 include those exemplified by R ⁰⁰³ with one hydrogen atom removed, and the like.

R ⁰⁰⁹ represents a monovalent hydrocarbon group containing a —CO ₂ — partial structure having 3 to 15 carbon atoms, specifically, 2-
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 containing a —CO ₂ — partial structure having 2 to 15 carbon atoms, and the rest are each independently a hydrogen atom or a straight chain having 1 to 15 carbon atoms. Represents a cyclic, 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-
Examples include oxooxolan-5-yloxycarbonyl and the like. Specific examples of the linear, branched, or cyclic alkyl group having 1 to 15 carbon atoms are the same as those exemplified for R ⁰⁰³ . R ^{010 to} R ⁰¹³ may combine with each other to form a ring, in which case at least one of R ^{01 0 to} R ⁰¹³ contains a —CO ₂ — partial structure having 1 to 15 carbon atoms. Represents a valent hydrocarbon group, and the rest 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 containing 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,
Other and 1,3-dioxo-2- Okisabutan-1,4-diyl, the -CO ₂ - partial structure those monovalent excluding one hydrogen atom from those exemplified in the hydrocarbon group containing such It can be illustrated. Specific examples of the linear, branched, or cyclic alkylene group having 1 to 15 carbon atoms include those exemplified by R ^{00 3} with one hydrogen atom removed, and the like.

R ⁰¹⁴ represents a polycyclic hydrocarbon group having 7 to 15 carbon atoms or an alkyl group containing a polycyclic hydrocarbon group,
Specific examples thereof 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 will be described later. Y represents -O- ^or- (NR ⁰¹⁶ )-, R ⁰¹⁶ represents a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms, and specifically, a methyl group or 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 cyclohexyl group, ethylcyclopentyl group, butylcyclopentyl group, ethylcyclohexyl group, butylcyclohexyl group, adamantyl group, ethyladamantyl group and butyladamantyl group. k is 0 or 1.

As the acid labile group of R ⁰¹⁵ , various ones can be used, but specifically, the following general formulas (L1) to (L
A group represented by 4), having 4 to 20 carbon atoms, preferably 4 to 1 carbon atoms
5 tertiary alkyl groups, each alkyl group has 1 carbon atom
Examples thereof include a trialkylsilyl group having 6 to 6 and an oxoalkyl group having 4 to 20 carbon atoms.

[0029]

[Chemical 12]

Here, the chain line indicates a bond (hereinafter the same). In the formula, R ^L01 and R ^L02 are a hydrogen atom or a carbon number of 1 to 1.
8, preferably 1-10 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
10 represents a monovalent hydrocarbon group which may have a hetero atom such as an oxygen atom, 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.

[0031]

[Chemical 13]

R ^L01 and R ^L02 , R ^L01 and R ^L03 , R ^L02 and R
^L03 may combine with each other to form a ring, and in the case of forming a ring, R ^L01 , R ^L02 and R ^L03 each have 1 carbon atom.
-18, preferably 1-10 linear or branched alkylene groups are shown.

R ^L04 has 4 to 20 carbon atoms, preferably 4 to 20 carbon atoms.
15 tertiary alkyl groups, each alkyl group represents 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 general formula (L1), and a tertiary alkyl group 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] heptan-2-yl) propan-2-yl group, 2- (adamantan-1-yl) propan-2-
Iyl 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 Examples thereof include 2-adamantyl group and 2-ethyl-2-adamantyl group. Specific examples of the trialkylsilyl group include trimethylsilyl group, triethylsilyl group, dimethyl-tert-butylsilyl group, and oxoalkyl. 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 having 1 to 8 carbon atoms which may contain a hetero atom or an optionally substituted aryl group having 6 to 20 carbon atoms which may contain a hetero atom. Specific examples of the hydrocarbon group of are methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, ter.
Linear, branched or cyclic alkyl groups such as t-amyl group, n-pentyl group, n-hexyl group, cyclopentyl group and cyclohexyl group, some of these hydrogen atoms are hydroxyl groups, alkoxy groups, carboxy groups, 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 aryl group which may be substituted include Examples thereof include a phenyl group, a methylphenyl group, a naphthyl group, an anthryl group, a phenanthryl group and a pyrenyl group. m is 0 or 1, n is 0, 1,
It is either 2, 3 or a number that satisfies 2m + n = 2 or 3.

R ^L06 represents a monovalent hydrocarbon group having 1 to 8 carbon atoms which may contain a hetero atom or an optionally substituted aryl group having 6 to 20 carbon atoms, which is specifically the same as R ^L05. And the like can be exemplified. R ^{L07 to} R ^L16 each independently represent a hydrogen atom or a monovalent hydrocarbon group which may contain a hetero atom 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 , A linear, branched or cyclic alkyl group such as a cyclohexylethyl group or a cyclohexylbutyl group, a part of these hydrogen atoms is a hydroxyl group, an alkoxy group, a carboxy group, an alkoxycarbonyl group, an oxo group, an amino group or an alkylamino group. Examples thereof include those substituted with groups, cyano groups, mercapto groups, alkylthio groups, sulfo groups and the like. R ^{L07 to} R ^L16 may combine with each other to form a ring (eg, 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). ,
R ^L13 , R ^L14, etc.), and in that case, a divalent hydrocarbon group having 1 to 15 carbon atoms which may contain a hetero atom. The thing which removed one atom etc. can be illustrated. Also, ^{RL07 to RL16}
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).

Among the acid labile groups represented by the above formula (L1), the straight-chain or branched groups are specifically exemplified by the following groups.

[0037]

[Chemical 14]

Specific examples of the cyclic acid-labile group represented by the above formula (L1) include tetrahydrofuran-2-yl group, 2-methyltetrahydrofuran-2-yl group and tetrahydropyran-2-yl group. Examples thereof include a group and a 2-methyltetrahydropyran-2-yl group.

Specific examples of the acid labile group of the above formula (L2) include tert-butoxycarbonyl group and 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, 1 -Sec-butylcyclopentyl, 1-cyclohexylcyclopentyl, 1- (4-methoxy-n-butyl) cyclopentyl, 1-methylcyclohexyl, 1-
Ethylcyclohexyl, 3-methyl-1-cyclopenten-3-yl, 3-ethyl-1-cyclopentene-3-
3-methyl-1-cyclohexen-3-yl, 3
Examples include -ethyl-1-cyclohexen-3-yl and the like. Specific examples of the acid labile group of the above formula (L4) include the following groups.

[0041]

[Chemical 15]

Further, a tertiary alkyl group having 4 to 20 carbon atoms,
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 the same as those listed for R ^L04 .

The repeating units represented by the above general formulas (M1) to (M9) impart various characteristics such as developer affinity, substrate adhesion and etching resistance when used as a resist material. By properly adjusting the content of the repeating unit, the performance of the resist material can be finely adjusted.

The weight average molecular weight of the polymer compound of the present invention is 1, when measured by gel permeation chromatography (GPC) in terms of polystyrene.
000 to 500,000, preferably 3,000 to 10
It is 10,000. If it is out of this range, the etching resistance may be extremely reduced, or the difference in dissolution rate before and after exposure may not be ensured, and the resolution may be lowered.

In the production of the polymer compound of the present invention, the compound represented by the following general formula (1a) is used as the first monomer, and the compound represented by the following general formula (2a) and / or (3a) is used as the first monomer. 2 or a second and a third monomer, and if necessary, one or more kinds selected from compounds represented by the following general formulas (M1a) to (M9a) are used for the subsequent monomers. It can be carried out by a conventional copolymerization reaction.

[0046]

[Chemical 16] (In the formula, R ^{1 to} R ¹¹ are the same as above.)

[0047]

[Chemical 17] (In the formula, k, R ^{001 to} R ⁰¹⁵ , X, and Y are the same as above.) In the copolymerization reaction, by adjusting the abundance ratio of each monomer as appropriate, preferable performance when used as a resist material A polymer compound capable of exhibiting

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 formula (2a) and / or (3a) (iii) the above formula ( In addition to the monomers M1a) to (M9a), (iv) a monomer containing a carbon-carbon double bond other than the above (i) to (iii), for example, methyl methacrylate,
Substituted acrylic acid esters such as methyl crotonate, dimethyl maleate and dimethyl itaconic acid, unsaturated carboxylic acids such as maleic acid, fumaric acid and itaconic acid, substituted norbornenes such as norbornene and norbornene-5-methyl carboxylate, anhydrous It does not matter if an unsaturated acid anhydride such as itaconic acid or another monomer is copolymerized.

In the polymer compound of the present invention, the preferable content ratio of each repeating unit based on each monomer is
For example, the repeating unit represented by the formula (1) based on the monomer of the formula (1a) is 1 to 90 mol%, preferably 5 to 80 mol%, more preferably 10 to 70 mol%, the formula (2a) and 5% of the repeating unit represented by the formula (2) and / or (3) based on the monomer of / or (3a)
90 mol%, preferably 10 to 80 mol%, more preferably 20 to 70 mol%, based on the monomer of formula (M1a) to (M9a) (M
1) to (M9) repeating units represented by 0 to 60 mol%, preferably 0 to 40 mol%, and more preferably 0 to 3 mol%.
0 mol%, 0 to other repeating units based on other monomers
60 mol%, preferably 0 to 40 mol%, more preferably 0 to 30 mol%, respectively,
It is not limited to this range.

The monomer of the general formula (1a), which is the basis of the unit of the general formula (1), which is essential for the polymer compound of the present invention, can be produced by the method described in JP-A-2000-159758. Further, as the monomers of the general formulas (2a) and (3a) which are the basis of the units of the general formulas (2) and (3), commercially available products can be used as they are, 2-adamantanone and 1- Using adamantane carboxylic acid esters as a raw material,
It can be produced in various ways using known organic chemistry techniques.

The copolymerization reaction for producing the polymer compound of the present invention can be variously exemplified, but radical polymerization is preferable.

The reaction conditions of the radical polymerization reaction are as follows: (a) hydrocarbons such as benzene, ethers such as tetrahydrofuran, alcohols such as ethanol, or ketones such as methyl isobutyl ketone as a solvent; An azo compound such as 2,2′-azobisisobutyronitrile or a peroxide such as benzoyl peroxide or lauroyl peroxide is used as an initiator, and (c) the reaction temperature is from 0 ° C. to 10 ° C.
Keep at 0 ℃, and (d) Reaction time from 0.5 hours to 48 hours
It is preferable to set the time to about time, but the case where the time is out of 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, particularly a chemically amplified positive resist material.

The resist material of the present invention may contain a compound which generates an acid in response to a high energy ray or an electron beam (hereinafter referred to as an acid generator), an organic solvent and, if necessary, other components. .

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 represented by the following general formula (P3), iv. A bissulfone derivative represented by the following general formula (P4), v. A sulfonic acid ester of an N-hydroxyimide compound represented by the following general formula (P5), vi. β-ketosulfonic acid derivative, vii. A disulfone derivative, viii. A nitrobenzyl sulfonate derivative, ix. Examples thereof include sulfonate ester derivatives.

[0056]

[Chemical 18] (In the formula, R ^101a , R ^101b , and R ^101c each have 1 to 10 carbon atoms.
12 represents a 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 hydrogen atoms of these groups may be substituted with an alkoxy group or the like. R ^101b and R ^101c may be bonded to each other to form a ring, and in the case of forming a ring, R ^101b and R ^101c each represent an alkylene group having 1 to 6 carbon atoms. K ⁻ represents a non-nucleophilic counter ion. )

The above 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, Examples thereof include an adamantyl group. 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,
Examples thereof include a 2- (4-methylcyclohexyl) -2-oxoethyl group. Examples of the aryl group include phenyl group, naphthyl group, p-methoxyphenyl group, m
-Methoxyphenyl group, o-methoxyphenyl group, ethoxyphenyl group, p-tert-butoxyphenyl group,
Alkoxyphenyl group such as m-tert-butoxyphenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, ethylphenyl group, 4-t
ert-butylphenyl group, 4-butylphenyl group, alkylphenyl group such as dimethylphenyl group, alkylnaphthyl group such as methylnaphthyl group, ethylnaphthyl group, alkoxynaphthyl group such as methoxynaphthyl group and ethoxynaphthyl group, dimethylnaphthyl group And a dialkylnaphthyl group such as a diethylnaphthyl group, a dialkoxynaphthyl group such as a dimethoxynaphthyl group, and a diethoxynaphthyl group. Examples of the aralkyl group include a benzyl group, a phenylethyl group and a phenethyl group. As the aryloxoalkyl group, a 2-phenyl-2-oxoethyl group, a 2- (1-naphthyl) -2-oxoethyl group, 2
Examples thereof include 2-aryl-2-oxoethyl groups such as-(2-naphthyl) -2-oxoethyl group. As the non-nucleophilic counter ion of K ⁻ , chloride ion, halide ion such as bromide ion, triflate, fluoroalkyl sulfonate such as 1,1,1-trifluoroethane sulfonate, nonafluorobutane sulfonate, tosylate, benzene sulfonate. Examples include aryl sulfonates such as 4-fluorobenzene sulfonate and 1,2,3,4,5-pentafluorobenzene sulfonate, and alkyl sulfonates such as mesylate and butane sulfonate.

[0058]

[Chemical 19] (In the formula, 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, and K ⁻ represents a non-nucleophilic counter ion.)

Specific examples of R ^102a and R ^102b include methyl group, ethyl group, propyl group, isopropyl group and n-
Examples thereof include a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a cyclopentyl group, a cyclohexyl group, a cyclopropylmethyl group, a 4-methylcyclohexyl group and a cyclohexylmethyl group. R ¹⁰³ is a methylene group,
Ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, 1,4-cyclohexylene group, 1,2-cyclohexylene group, 1,3-cyclopentyl group 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 represented by the formulas (P1a-1) and (P1a-
The same thing as what was demonstrated by 2) can be mentioned.

[0060]

[Chemical 20] (In the formula, R ¹⁰⁵ and R ¹⁰⁶ are linear, branched or cyclic alkyl groups having 1 to 12 carbon atoms or halogenated alkyl groups, aryl groups having 6 to 20 carbon atoms or halogenated aryl groups,
Alternatively, it represents an aralkyl group having 7 to 12 carbon atoms. )

The alkyl groups represented by R ¹⁰⁵ and R ¹⁰⁶ include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group. Group, amyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, norbornyl group, adamantyl group and the like. As the halogenated alkyl group, trifluoromethyl group, 1,1,1-trifluoroethyl group, 1,1,1-
Examples thereof include trichloroethyl group and nonafluorobutyl group. As the aryl group, a phenyl group, a p-methoxyphenyl group, an m-methoxyphenyl group, an o-methoxyphenyl group, an ethoxyphenyl group, an alkoxyphenyl group such as a p-tert-butoxyphenyl group and an m-tert-butoxyphenyl group, Examples thereof include alkylphenyl groups such as 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, ethylphenyl group, 4-tert-butylphenyl group, 4-butylphenyl group and 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.

[0062]

[Chemical 21] (In the formula, R ¹⁰⁷ , R ¹⁰⁸ , and R ¹⁰⁹ are linear, branched, or cyclic alkyl groups having 1 to 12 carbon atoms or halogenated alkyl groups, aryl groups having 6 to 20 carbon atoms, or halogenated aryl groups, Alternatively, it represents an aralkyl group having 7 to 12 carbon atoms.
¹⁰⁸ and R ¹⁰⁹ may combine with each other to form a cyclic structure, and in the case of forming a cyclic structure, R ¹⁰⁸ and R ¹⁰⁹ each represent a linear or branched alkylene group having 1 to 6 carbon atoms. )

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 those described for R ¹⁰⁵ and R ¹⁰⁶ . ^Examples of the alkylene group for R ¹⁰⁸ and R ¹⁰⁹ include a methylene group, an ethylene group, a propylene group, a butylene group and a hexylene group.

[0064]

[Chemical formula 22] (In the formula, R ^101a and R ^101b are the same as above.)

[0065]

[Chemical formula 23] (In the formula, 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 are carbon atoms. It may be substituted with a linear or branched alkyl group or alkoxy group having 1 to 4 carbon atoms, a nitro group, an acetyl group, or a phenyl group, R ¹¹¹ is a linear or branched carbon atom having 1 to 8 carbon atoms. Or a substituted alkyl group, an alkenyl group or an alkoxyalkyl group, a phenyl group, or a naphthyl group, and some or all of the hydrogen atoms of these groups are further an alkyl group or an alkoxy group having 1 to 4 carbon atoms; A phenyl group which may be substituted with an alkyl group, an alkoxy group, a nitro group or an acetyl group having 4 to 4; a heteroaromatic group having 3 to 5 carbon atoms; or a chlorine atom and a fluorine atom which may be substituted).

Here, as the arylene group of R ¹¹⁰ ,
1,2-phenylene group, 1,8-naphthylene group and the like, and alkylene groups include methylene group, ethylene group, trimethylene group, tetramethylene group, phenylethylene group, norbornane-2,3-diyl group and the like, alkenylene. As the group, 1,2-vinylene group, 1-phenyl-1,2-
Examples thereof include vinylene group and 5-norbornene-2,3-diyl group. ^Examples of the alkyl group of R ¹¹¹ include R ^{101a to} R
Similar to ^101c , the alkenyl group includes vinyl group, 1-propenyl group, allyl group, 1-butenyl group, 3
-Butenyl group, isoprenyl group, 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 and the like, As the alkoxyalkyl group, a methoxymethyl group, an ethoxymethyl group,
Propoxymethyl group, butoxymethyl group, pentyloxymethyl group, hexyloxymethyl group, heptyloxymethyl group, methoxyethyl group, ethoxyethyl group, propoxyethyl group, butoxyethyl group, pentyloxyethyl group,
Hexyloxyethyl group, methoxypropyl group, ethoxypropyl group, propoxypropyl group, butoxypropyl group, methoxybutyl group, ethoxybutyl group, propoxybutyl group, methoxypentyl group, ethoxypentyl group,
Examples thereof include a methoxyhexyl group and a methoxyheptyl group.

The number of carbon atoms which may be further substituted is 1
As the alkyl group of 4 to 4, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, and the like, and as an alkoxy group having 1 to 4 carbon atoms, a methoxy group, an ethoxy group. Group, propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, tert-butoxy group and the like, a phenyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms, an alkoxy group, a nitro group or an acetyl group. Examples of the phenyl group, tolyl group, p-tert-butoxyphenyl group, p-acetylphenyl group, p-nitrophenyl group and the like have a carbon number of 3 to
Examples of the heteroaromatic group of 5 include a pyridyl group and a furyl group.

Specifically, for example, diphenyliodonium trifluoromethanesulfonate, (p-tert-butoxyphenyl) phenyliodonium trifluoromethanesulfonate, diphenyliodonium p-toluenesulfonate, p-toluenesulfonic acid (p-tert-).
Butoxyphenyl) phenyliodonium, triphenylsulfonium trifluoromethanesulfonate, trifluoromethanesulfonate (p-tert-butoxyphenyl) diphenylsulfonium, bis (p-tert-butoxyphenyl) phenylsulfonium trifluoromethanesulfonate, trifluoromethanesulfonate tris (P-tert-butoxyphenyl) sulfonium,
Triphenylsulfonium p-toluenesulfonate, p
-Toluenesulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, p-toluenesulfonic acid bis (p-tert-butoxyphenyl) phenylsulfonium, p-toluenesulfonic acid tris (p-ter)
t-butoxyphenyl) sulfonium, triphenylsulfonium nonafluorobutanesulfonate, triphenylsulfonium butanesulfonate, trimethylsulfonium trifluoromethanesulfonate, trimethylsulfonium p-toluenesulfonate, cyclohexylmethyl trifluoromethanesulfonate (2-oxocyclohexyl) Sulfonium, cyclohexylmethyl (2-oxocyclohexyl) sulfonium p-toluenesulfonate, dimethylphenylsulfonium trifluoromethanesulfonate, dimethylphenylsulfonium p-toluenesulfonate, dicyclohexylphenylsulfonium trifluoromethanesulfonate, dicyclohexylphenylsulfonium p-toluenesulfonate , Trifluoromethanesulfone Trinaphthylsulfonium, cyclohexylmethyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, (2-norbornyl) methyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, ethylenebis [methyl (2-oxocyclopentyl) sulfonium trifluoromethanesulfone Nato], 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-
Amylsulfonyl) diazomethane, 1-tert-amylsulfonyl-1- (tert-butylsulfonyl) diazomethane and other diazomethane derivatives, bis-O- (p-
Toluenesulfonyl) -α-dimethylglyoxime, bis-O- (p-toluenesulfonyl) -α-diphenylglyoxime, bis-O- (p-toluenesulfonyl)
-Α-dicyclohexyl glyoxime, 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, 2
-Cyclohexylcarbonyl-2- (p-toluenesulfonyl) propane, 2-isopropylcarbonyl-2-
Β-ketosulfone derivative such as (p-toluenesulfonyl) propane, disulfone derivative such as diphenyldisulfone and dicyclohexyldisulfone, 2,6-dinitrobenzyl p-toluenesulfonate, nitro such as 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, etc. Sulfonate derivative, N-hydroxysuccinimide methanesulfonate, N-hydroxysuccinimide trifluoromethanesulfonate, N-hydroxysuccinimideethanesulfonate, 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-toluene sulfone Acid ester, N-
Hydroxysuccinimide p-methoxybenzenesulfonic acid ester, N-hydroxysuccinimide 2-chloroethanesulfonic acid ester, N-hydroxysuccinimide benzenesulfonic acid ester, N-hydroxysuccinimide-2,4,6-trimethylbenzenesulfonic acid ester, N-hydroxy Succinimide 1-naphthalene sulfonate, N-hydroxysuccinimide 2-naphthalene sulfonate, N-hydroxy-2-phenyl succinimide methane sulfonate, N-hydroxy maleimide methane sulfonate, N-hydroxy maleimide ethane sulfonate, 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-dicarboximidomethanesulfonic acid ester , N-hydroxy-5-norbornene-2,3-dicarboximide trifluoromethanesulfonic acid ester, N-hydroxy-5-norbornene-2,3-dicarboximide p-toluenesulfonic acid ester, etc.
Examples thereof include sulfonic acid ester derivatives of hydroxyimide compounds, and trifluoromethanesulfonic acid triphenylsulfonium, trifluoromethanesulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, trifluoromethanesulfonic acid tris (pt).
ert-butoxyphenyl) sulfonium, p-toluenesulfonate triphenylsulfonium, p-toluenesulfonate (p-tert-butoxyphenyl) diphenylsulfonium, p-toluenesulfonate tris (p
-Tert-butoxyphenyl) sulfonium, trinaphthylsulfonium trifluoromethanesulfonate, cyclohexylmethyl trifluoromethanesulfonate (2
-Oxocyclohexyl) sulfonium, (2-norbornyl) methyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, onium salts such as 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 and 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,
Sulfonic acid ester derivatives of N-hydroxyimide compounds such as N-hydroxynaphthalimide methanesulfonic acid ester and N-hydroxynaphthalimidobenzenesulfonic acid ester are preferably used. In addition, the said acid generator can be used individually by 1 type or in combination of 2 or more types. Since the onium salt is excellent in the rectangularity improving effect and the diazomethane derivative and the glyoxime derivative are excellent in the standing wave reducing effect, it is possible to finely adjust the profile by combining them.

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

The organic solvent used in the present invention may be any organic solvent in which the base resin, acid generator, other additives and the like can be dissolved. Examples of such an organic solvent include ketones such as cyclohexanone and methyl-2-n-amyl ketone, 3-methoxybutanol, and 3
-Methyl-3-methoxybutanol, 1-methoxy-2
-Alcohols such as propanol and 1-ethoxy-2-propanol, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether and other ethers, 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.
Examples thereof include esters such as t-butyl ether acetate, and one of these may be used alone or two or more of them may be used in combination, but the present invention is not limited thereto. In the present invention, among these organic solvents, in addition to diethylene glycol dimethyl ether and 1-ethoxy-2-propanol, which have the best solubility of the acid generator in the resist component, propylene glycol monomethyl ether acetate which is a safe solvent and a mixture thereof. Solvents are preferably used.

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

A polymer compound other than the polymer compound of the present invention can be added to the resist material of the present invention. Specific examples of the polymer compound include the following formula (R
1) and / or a weight average molecular weight represented by the following formula (R2) of 1,000 to 500,000, preferably 5,000.
However, the present invention is not limited to these.

[0073]

[Chemical formula 24] (In the formula, R ⁰⁰¹ is a hydrogen atom, a methyl group or CH ₂ CO ₂ R
Indicates ⁰⁰³ . R ⁰⁰² is a hydrogen atom, a methyl group or CO ₂ R ⁰⁰³
Indicates. R ⁰⁰³ represents a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms. R ⁰⁰⁴ represents a hydrogen atom, a carboxy group having 1 to 15 carbon atoms, or a monovalent hydrocarbon group containing a hydroxyl group. At least one of R ^{005 to} R ^{008 represents} a monovalent hydrocarbon group having a carboxy group having 1 to 15 carbon atoms or a hydroxyl group, and the rest independently represent a hydrogen atom or a straight chain having 1 to 15 carbon atoms, A branched or cyclic alkyl group is shown. R ^{005 to} R ⁰⁰⁸ may combine with each other to form a ring, in which case at least one of R ^{005 to} R ⁰⁰⁸ is a divalent carbon atom containing a carboxy group or a hydroxyl group having 1 to 15 carbon atoms. A hydrogen group is shown, and the rest are each independently a single bond or a linear, branched or cyclic alkylene group having 1 to 15 carbon atoms. R ⁰⁰⁹ represents a monovalent hydrocarbon group containing a —CO ₂ — partial structure having 3 to 15 carbon atoms. R ^{0 10 to} R ⁰¹³
At least 1 represents a monovalent hydrocarbon group containing a —CO ₂ — partial structure having 2 to 15 carbon atoms, and the rest each independently represents a hydrogen atom or a straight chain, branched or 1 to 15 carbon atom. A cyclic alkyl group is shown. R ⁰¹⁰ to R ⁰¹³ may be bonded to each other to form a ring, in which case R ⁰¹⁰ to R
^At least one of ^C 13 s represents a divalent hydrocarbon group containing a —CO ₂ — partial structure having 1 to 15 carbon atoms, and the rest are each independently a single bond or a linear or branched C 1 to 15 carbon atom. Alternatively, it represents a cyclic alkylene group. R ⁰¹⁴ has 7 to 15 carbon atoms
Represents a polycyclic hydrocarbon group 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 is CH ₂
Or represents an oxygen atom. k ′ is 0 or 1. a1 ',
a2 ', a3', b1 ', b2', b3 ', c1', c
2 ', c3', d1 ', d2', d3 ', e'are numbers of 0 or more and less than 1, a1' + a2 '+ a3' + b1 '+
b2 '+ b3' + c1 '+ c2' + c3 '+ d1' + d
2 ′ + d3 ′ + e ′ = 1 is satisfied. f ', g',
h ', i', j'are numbers greater than or equal to 0 and less than 1, and f '+
g ′ + h ′ + i ′ + j ′ = 1 is satisfied. x ', y',
z ′ is an integer of 0 to 3, and 1 ≦ x ′ + y ′ + z ′ ≦
5, 1 ≦ y ′ + z ′ ≦ 3 is satisfied. ) Note that specific examples of each group are the same as those described above.

The compounding ratio of the polymer compound of the present invention to another polymer compound is from 100: 0 to 10:90, especially 10
It is preferably within the range of the weight ratio of 0: 0 to 20:80. If the compounding ratio of the polymer compound of the present invention is lower than this range, the desired performance as a resist material may not be obtained. The performance of the resist material can be adjusted by appropriately changing the above compounding ratio.

The polymer compound is not limited to one type,
More than one species can be added. The performance of the resist material can be adjusted by using plural kinds of polymer compounds.

A dissolution control agent can be further added to the resist material of the present invention. The dissolution control 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, in which the hydrogen atom of the phenolic hydroxyl group is substituted with an acid labile group at an average rate of 0 to 100 mol% or a carboxy group in the molecule A compound in which the hydrogen atom of the carboxy group of the compound having is substituted with an acid labile group at an average of 50 to 100 mol% is compounded.

The substitution ratio of the hydrogen atom of the phenolic hydroxyl group with the acid labile group is 0 mol% or more, preferably 30 mol% or more of the whole 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 with the acid labile group is 50 mol% or more, preferably 70 mol% or more of the entire carboxy group on average, and the upper limit thereof is 100 mol%.
Is.

In this case, the phenolic hydroxyl group is 2
As the compound having three or more or the compound having a carboxy group, compounds represented by the following formulas (D1) to (D14) are preferable.

[0079]

[Chemical 25] (However, in the formula R²⁰¹, R²⁰²Are hydrogen atom or charcoal
Linear or branched alkyl group or alkene having a prime number of 1 to 8
Indicates a nyl group. R²⁰³Is a hydrogen atom or having 1 to 8 carbon atoms
A linear or branched alkyl or alkenyl group,
Iha- (R²⁰⁷)_hIndicates COOH. R²⁰⁴Is-(CH₂)
_i-(I = 2 to 10), arylene having 6 to 10 carbon atoms
Group, carbonyl group, sulfonyl group, oxygen atom or sulfur atom
Indicates a child. R ²⁰⁵Is an alkylene group having 1 to 10 carbon atoms, charcoal
Arylene groups, carbonyl groups, and sulfonis having a prime number of 6 to 10
Group, oxygen atom or sulfur atom. R²⁰⁶Is hydrogen
Child, a linear or branched alkyl group having 1 to 8 carbon atoms,
Phenyl substituted with a lukenyl group or a hydroxyl group
Represents a group or a naphthyl group. R²⁰⁷Is a straight chain of 1 to 10 carbon atoms
A chain or branched alkylene group is shown. R²⁰⁸Is hydrogen
Indicates a child or a hydroxyl group. j is an integer of 0-5. u, h
Is 0 or 1. s, t, s ', t', s ",
t ″ is s + t = 8, s ′ + t ′ = 5, s ″, respectively.
+ T ″ = 4 and less in each phenyl skeleton
Both are numbers having one hydroxyl group. α is the formula (D
8), the molecular weight of the compound (D9) is 100 to 1,000.
And the number. )

In the above formula, R ²⁰¹ and R ²⁰² are, for example, hydrogen atom, methyl group, ethyl group, butyl group, propyl group,
Ethynyl group, a cyclohexyl group, the R ^203, for example, those similar to R ^{2 01,} R ^202, or -COOH, -
Examples of CH ₂ COOH and R ²⁰⁴ include an ethylene group, a phenylene group, a carbonyl group, a sulfonyl group, an oxygen atom,
A sulfur atom or the like, R ²⁰⁵ is, for example, a methylene group or the same as R ^204, and R ²⁰⁶ is, for example, a hydrogen atom, a methyl group, an ethyl group, a butyl group, a propyl group, an ethynyl group, a cyclohexyl group or a hydroxyl group. Examples thereof include a substituted phenyl group and naphthyl group.

Various types of acid labile groups can be used as the acid labile group of the dissolution control agent. Specifically, specific examples of the following general formula (L1)
Examples include a 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.

[0082]

[Chemical formula 26] (In the formula, R^L01, R^L02Is a hydrogen atom or a C1-18
A linear, branched or cyclic alkyl group is shown. R^L03Is
It may have a hetero atom such as an oxygen atom having 1 to 18 carbon atoms.
Represents a monovalent hydrocarbon group. R^L01And R^L02, R^L01And R
^L03, R^L02And R^L03And are bonded to each other to form a ring
Well, when forming a ring, R^L01, R^L02, R^L03Haso
Linear or branched alkylene having 1 to 18 carbon atoms, respectively
Indicates 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 ryl group, an oxoalkyl group having 4 to 20 carbon atoms, or one of the above.
The group represented by formula (L1) is shown. R^L05Has 1 to 1 carbon atoms
Monovalent hydrocarbon radicals or charcoals which may contain 8 heteroatoms
Shows an optionally substituted aryl group having a prime number of 6 to 20.
You R^L06May contain a hetero atom having 1 to 8 carbon atoms
Monovalent hydrocarbon group or substituted with 6 to 20 carbon atoms
Is an aryl group. R^L07~ R^L16Are independent
To a hydrogen atom or a hetero atom having 1 to 15 carbon atoms
It shows a good monovalent hydrocarbon group. R^L07~ R^L16Tied to each other
May combine with each other to form a ring, in which case the carbon number is 1
A divalent hydrocarbon group which may contain ~ 15 heteroatoms
Show. Also, R ^L07~ R^L16Also binds to adjacent carbons
It is also possible to form a double bond by binding with each other without any intervention.
Yes. y is an integer of 0-6. m is 0 or 1, n is 0,
Either 1, 2, or 3 and 2m + n = 2 or 3 is satisfied
It is the number to add. ) Note that specific examples of each group are the same as those described above.
It is like.

The amount of the above dissolution control agent to be added is based on the base resin 1
It is 0 to 50 parts, preferably 0 to 40 parts, more preferably 0 to 30 parts, relative to 00 parts, and they can be used alone or in combination of two or more. If the blending amount exceeds 50 parts, the pattern film may be reduced and the resolution may be lowered.

The above-mentioned dissolution control agent is used for compounds having a phenolic hydroxyl group or a carboxy group,
Synthesized by introducing acid labile groups using organic chemistry recipes.

Further, a basic compound can be added to the resist material of the present invention. As the basic compound, a compound that can suppress the diffusion rate when the acid generated from the acid generator diffuses in the resist film is suitable. By compounding a basic compound, the acid diffusion rate in the resist film is suppressed and the resolution is improved, sensitivity changes after exposure are suppressed, and substrate and environmental dependence are reduced, and exposure margin and pattern profile are reduced. Etc. can be improved.

Examples of such a basic compound include primary, secondary and tertiary aliphatic amines, mixed amines,
Aromatic amines, heterocyclic amines, nitrogen-containing compounds having a carboxy group, nitrogen-containing compounds having a sulfonyl group,
Examples thereof include nitrogen-containing compounds having a hydroxyl group, nitrogen-containing compounds having a hydroxyphenyl group, alcoholic nitrogen-containing compounds, amide derivatives and imide derivatives.

Specifically, as the primary aliphatic amines, ammonia, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, ter.
t-butylamine, pentylamine, tert-amylamine, cyclopentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine,
Nonylamine, decylamine, dodecylamine, cetylamine, methylenediamine, ethylenediamine, tetraethylenepentamine, etc. are exemplified, and secondary aliphatic amines include 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 are exemplified, and as tertiary aliphatic amines, trimethylamine, triethylamine, tri-n-propylamine, 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 (eg, 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-
Dimethyltoluidine), diphenyl (p-tolyl) amine, methyldiphenylamine, triphenylamine,
Phenylenediamine, naphthylamine, diaminonaphthalene, pyrrole derivatives (eg pyrrole, 2H-pyrrole, 1-methylpyrrole, 2,4-dimethylpyrrole,
2,5-dimethylpyrrole, N-methylpyrrole, etc.),
Oxazole derivatives (such as oxazole and isoxazole), thiazole derivatives (such as thiazole and isothiazole), imidazole derivatives (such as imidazole, 4-methylimidazole and 4-methyl-2-phenylimidazole), pyrazole derivatives, furazan derivatives, Pyrroline derivative (for example, pyrroline, 2-methyl-1-pyrroline, etc.), Pyrrolidine derivative (for example, pyrrolidine, N-methylpyrrolidine, pyrrolidinone, N-methylpyrrolidone, etc.), imidazoline derivative, imidazolidine derivative, pyridine derivative (for example, pyridine, methyl) Pyridine, ethyl pyridine, propyl pyridine, butyl pyridine, 4- (1-butylpentyl) pyridine, dimethyl pyridine, trimethyl pyridine, triethyl pyridine, phenyl pyridi , 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 derivative, pyrimidine derivative, pyrazine derivative, pyrazoline derivative, pyrazolidine derivative, piperidine derivative, piperazine derivative, morpholine derivative, indole derivative, isoindole derivative, 1H-indazole derivative, indoline derivative, quinoline derivative (For example, quinoline, 3-quinolinecarbonitrile, etc.), isoquinoline derivative, cinnoline derivative, quinazoline derivative, quinoxaline derivative, phthalazine derivative, purine derivative, pteridine derivative, carbazole derivative, phenanthridine derivative, acridine derivative, phenazine derivative, 1,1
Examples thereof include 0-phenanthroline derivative, adenine derivative, adenosine derivative, guanine derivative, guanosine derivative, uracil derivative and uridine derivative.

Further, examples of the nitrogen-containing compound having a carboxy group include aminobenzoic acid, indolecarboxylic acid, amino acid derivatives (for example, 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, and 3-pyridinesulfonic acid as a nitrogen-containing compound having a sulfonyl group, P-toluenesulfonate pyridinium and the like are exemplified, and as the nitrogen-containing compound having a hydroxyl group, the nitrogen-containing compound having a hydroxyphenyl group, and the alcoholic nitrogen-containing compound, 2-hydroxypyridine, aminocresol, 2,4-quinolinediol, 3-indole methanol hydrate, monoethanolamine, diethanolamine, triethanolamine, N-ethyldiethanolamine, N, N-diethylethanolamine, triisopropanolamine,
2,2'-iminodiethanol, 2-aminoethano-
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, piperidine ethanol, 1- (2-hydroxyethyl) pyrrolidine,
1- (2-hydroxyethyl) -2-pyrrolidinone, 3
-Piperidino-1,2-propanediol, 3-pyrrolidino-1,2-propanediol, 8-hydroxyjulolidine, 3-cuinclidinol, 3-tropanol,
1-Methyl-2-pyrrolidine ethanol, 1-aziridine ethanol, N- (2-hydroxyethyl) phthalimide, N- (2-hydroxyethyl) isonicotinamide and the like are exemplified. Examples of the amide derivative include formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N,
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 the basic compounds represented by the following general formula (B1) can be blended.

[0091]

[Chemical 27] (In the formula, n = 1, 2 or 3. Y each independently represents a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and may contain a hydroxyl group or an ether structure. Each X independently represents a group represented by the following general formulas (X1) to (X3), and two or three X's may combine to form a ring.)

[0092]

[Chemical 28] (In the formula, R ³⁰⁰ , R ³⁰² , and R ^{305 each} represent a linear or branched alkylene group having 1 to 4 carbon atoms. R ³⁰¹ and R ^{304 each} represent a hydrogen atom, or a linear chain having 1 to 20 carbon atoms, It represents a branched or cyclic alkyl group, and may contain one or more of a hydroxy group, an ether structure, an ester structure, or a lactone ring, R ³⁰³ is a single bond or a straight chain or branched chain having 1 to 4 carbon atoms. Represents an alkylene group of

Specific examples of the basic compound represented by the above general formula (B1) include tris (2-methoxymethoxyethyl) amine and tris {2- (2-methoxyethoxy).
Ethyl} amine, tris {2- (2-methoxyethoxymethoxy) ethyl} amine, tris {2- (1-methoxyethoxy) ethyl} amine, tris {2- (1-ethoxyethoxy) ethyl} amine, tris {2 -(1-Ethoxypropoxy) ethyl} amine, tris [2- {2
-(2-Hydroxyethoxy) ethoxy} ethyl] amine, 4,7,13,16,21,24-hexaoxa-
1,10-diazabicyclo [8.8.8] hexacosane, 4,7,13,18-tetraoxa-1,10-diazabicyclo [8.5.5] eicosane, 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 ( Two
-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) Examples thereof include -δ-valerolactone.

Further, one or more selected from basic compounds having a cyclic structure represented by the following general formula (B2) can be blended.

[0095]

[Chemical 29] (In the formula, X is the same as above. R ³⁰⁷ has 2 to 2 carbon atoms.
It is a linear or branched alkylene group of 0 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 above 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,
Acetoxyacetic acid 2-morpholinoethyl, 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 morpholino propionate, 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 , Methyl thiomorpholino acetate, ethyl 1-pyrrolidinyl acetate, and 2-methoxyethyl morpholino acetate.

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

[0098]

[Chemical 30] (In the formula, X, R ³⁰⁷ and n are the same as above. R ³⁰⁸ and R
Each ³⁰⁹ is independently a linear or branched alkylene group having 1 to 4 carbon atoms. )

Specific examples of the basic compound having a cyano group represented by the above 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, N- (2-cyanoethyl) -N- (2-methoxyethyl) -3-aminopropionic acid methyl ester , Methyl N- (2-cyanoethyl) -N- (2-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, methyl N-cyanomethyl-N- (2-methoxyethyl) -3-aminopropionate, methyl N-cyanomethyl-N- (2-hydroxyethyl) -3-aminopropionate, N
-(2-acetoxyethyl) -N-cyanomethyl-3-
Methyl aminopropionate, 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-piperidinepropionate Ononitrile, 4-morpholine propiononitrile, 1-pyrrolidine acetonitrile, 1-piperidine acetonitrile, 4-morpholine acetonitrile, cyanomethyl 3-diethylaminopropionate, N, N-bis (2-hydroxyethyl)-
Cyanomethyl 3-aminopropionate, N, N-bis (2-acetoxyethyl) -3-aminopropionate cyanomethyl, N, N-bis (2-formyloxyethyl) -3-aminopropionate cyanomethyl, N, N-
Bis (2-methoxyethyl) -3-aminopropionate cyanomethyl, N, N-bis [2- (methoxymethoxy) ethyl] -3-aminopropionate cyanomethyl,
3-Diethylaminopropionic acid (2-cyanoethyl), N, N-bis (2-hydroxyethyl) -3-aminopropionic acid (2-cyanoethyl), N, N-bis (2-acetoxyethyl) -3-aminopropion 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), 1-pyrrolidine cyanomethyl propionate, 1-piperidine cyanomethyl propionate, 4-morpholine cyanomethyl propionate ,
1-pyrrolidine propionic acid (2-cyanoethyl), 1
-Piperidine propionic acid (2-cyanoethyl), 4-
Morpholine propionic acid (2-cyanoethyl) etc. can be illustrated.

The amount of the basic compound to be added is such that the acid generator 1
0.001-10 parts, preferably 0.01-
It is one copy. If the blending 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 decrease.

Further, the resist material of the present invention may contain a compound having a group represented by ≡C-COOH in the molecule.

As the compound having a group represented by ≡C-COOH in the molecule, for example, one kind or two or more kinds of compounds selected from the following group I and group II can be used, but the compounds 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] Some or all of the hydrogen atoms of the phenolic hydroxyl group of the compounds represented by the following general formulas (A1) to (A10) are -R ⁴⁰¹ -COOH (R ⁴⁰¹ is a straight chain having 1 to 10 carbon atoms or A branched alkylene group), and the molar ratio of the phenolic hydroxyl group (C) in the molecule to the group (D) represented by ≡C—COOH is C / (C + D) = 0.1.
A compound that is ˜1.0. [Group II] Compounds represented by the following general formulas (A11) to (A15).

[0103]

[Chemical 31] (However, in the formula, R ⁴⁰⁸ represents a hydrogen atom or a methyl group.
⁴⁰² and R ⁴⁰³ each represent a hydrogen atom or a linear or branched alkyl group or alkenyl group having 1 to 8 carbon atoms. R
⁴⁰⁴ is a hydrogen atom or a linear or branched alkyl group or alkenyl group having 1 to 8 carbon atoms, or-( ^R409 ) _h-
COOR 'group (R' is a hydrogen atom or an -R ^{40 9} -COO
H) is shown. R ⁴⁰⁵ is _{- (CH 2) i - (} i = 2~1
0), an arylene group having 6 to 10 carbon atoms, a carbonyl group,
A sulfonyl group, an oxygen atom or a sulfur atom is shown. R ⁴⁰⁶ 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 ⁴⁰⁷ represents a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, an alkenyl group, a phenyl group substituted with a hydroxyl group, or a naphthyl 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
^R411- 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, s
2, t2, s3, t3, s4, t4 are each s1 + t
1 = 8, s2 + t2 = 5, s3 + t3 = 4, s4 + t4
= 6 and has at least one hydroxyl group in each phenyl skeleton. κ is the number that gives the compound of formula (A6) a weight average molecular weight of 1,000 to 5,000. λ is the weight average molecular weight of the compound of formula (A7) 1,
The number is 000 to 10,000. )

[0104]

[Chemical 32] (R ⁴⁰² , R ⁴⁰³ and R ⁴¹¹ have the same meanings as described above. R
⁴¹² represents a hydrogen atom or a hydroxyl group. s5 and t5 are s5
It is a number satisfying s5 + t5 = 5 when ≧ 0 and t5 ≧ 0. h ′ is 0 or 1. )

As this component, specifically, the following general formula AI
Examples thereof include compounds represented by -1 to 14 and AII-1 to 10, but are not limited thereto.

[0106]

[Chemical 33] (R "represents a hydrogen atom or a CH ₂ COOH group, and 10 to 100 mol% of R" in each compound is CH ₂ CO
It is an OH group. α and κ have the same meanings as above. )

[0107]

[Chemical 34]

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

The addition 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, and more preferably 0.1 part to 100 parts of the base resin. -3 parts, more preferably 0.1-2 parts. 5
If it is larger than the area, the resolution of the resist material may decrease.

Further, the resist material of the present invention may contain an acetylene alcohol derivative as an additive, which can improve the storage stability.

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

[0112]

[Chemical 35] (In the formula, 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. )

The acetylene alcohol derivative is preferably Surfynol 61, Surfynol 82, Surfynol 104, Surfynol 104E, Surfynol 104H, Surfynol 104A, Surfynol TG, Surfynol PC, Surfynol 44.
0, Surfynol 465, Surfynol 485 (A
ir Products and Chemicals
Inc. Manufactured by Nisshin Chemical Industry Co., Ltd., and the like.

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

In addition to the above components, the resist composition of the present invention may contain, as an optional component, a surfactant which is commonly used for improving the coating property. In addition, the addition amount of the optional component can be a normal amount within a range that does not impair the effects of the present invention.

Here, the surfactant is preferably a nonionic one, such as perfluoroalkyl polyoxyethylene ethanol, fluorinated alkyl ester, perfluoroalkylamine oxide, perfluoroalkyl EO adduct, fluorine-containing organosiloxane system. A compound etc. are mentioned. For example, Florard "FC-430", "F
C-431 "(all manufactured by Sumitomo 3M Limited), Surflon" S-141 "," S-145 "," KH-1 "
0 "," KH-20 "," KH-30 "," KH-4 "
0 "(all manufactured by Asahi Glass Co., Ltd.), Unidyne" DS- "
401 "," DS-403 "," DS-451 "(all manufactured by Daikin Industries, Ltd.), Megafac" F-81 "
51 "(manufactured by Dainippon Ink Industry Co., Ltd.)," X-70-0 "
92 "," X-70-093 "(all manufactured by Shin-Etsu Chemical Co., Ltd.) and the like. Preferably, Florard "FC-430" (manufactured by Sumitomo 3M Limited),
Examples thereof include “KH-20”, “KH-30” (all manufactured by Asahi Glass Co., Ltd.), and “X-70-093” (manufactured by Shin-Etsu Chemical Co., Ltd.).

A pattern can be formed by using the resist material of the present invention by adopting a known lithography technique. For example, a film such as a silicon wafer can be formed by spin coating or the like to a film thickness of 0. .2-2.0μ
m so that it becomes 60 m on a hot plate.
~ 150 ° C, 1 to 10 minutes, preferably 80 to 130
Prebak at 1 ° C for 1 to 5 minutes. Next, a mask for forming a target pattern is held over the resist film, and a high energy ray such as deep ultraviolet ray, excimer laser, or X-ray or electron beam is exposed at an exposure amount of about 1 to 200 mJ / cm ² , preferably 5 to 5. After irradiating so as to be about 100 mJ / cm ² , 60 to 150 ° C. on a hot plate, 1
Post exposure bake (PEB) is performed for 5 minutes, preferably 80 to 130 ° C. for 1 to 3 minutes. Furthermore, 0.1
~ 5%, preferably 2-3% tetramethylammonium hydroxide (TMAH) in an alkaline aqueous solution developer, 0.1-3 minutes, preferably 0.5-2 minutes,
A desired pattern is formed on the substrate by developing by a conventional method such as a dipping method, a puddle method, or a spray method. In addition, the material of the present invention is 248 to 193 nm even in high energy rays.
Most suitable for fine patterning with deep ultraviolet rays or excimer laser, X-ray and electron beam. If the above range falls outside the upper and lower limits, the desired pattern may not be obtained.

[0118]

EFFECTS OF THE INVENTION The resist material using the polymer compound of the present invention as a base resin is sensitive to high energy rays, and is excellent in sensitivity, resolution and etching resistance, so that it is suitable for fine processing by electron beams or deep ultraviolet rays. It is useful. In particular, since the absorption at the exposure wavelength of ArF excimer laser and KrF excimer laser is small, it has a feature that a fine pattern can be easily formed perpendicular to the substrate.

[0119]

EXAMPLES The present invention will be described in detail 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 1 112.0 g of 3-oxo-2,7-dioxatricyclo [4.2.1.0 ^4,8 ] nonan-9-yl methacrylate, 117.0 g of methacrylic acid 2-Methyl-2-adamantyl, 1.40 g 2-mercaptoethanol and 763.3 g tetrahydrofuran were mixed. The reaction mixture is heated to 60 ° C. and 3.28 g of 2,2′-
Azobisisobutylnitrile was added, and the mixture was stirred for 15 hours while maintaining 60 ° C. After cooling to room temperature, 500 ml
Of acetone and was added dropwise to 10 L of isopropyl alcohol with vigorous stirring. The resulting solid matter was collected by filtration and vacuum dried at 40 ° C. for 15 hours to obtain a white powder solid polymer compound represented by the following formula Polymer1. The yield was 183.9 g, and the yield was 80.3.
%Met. In addition, Mw is GP in terms of polystyrene
The weight average molecular weight measured using C is shown.

[Synthesis Examples 2 to 12] Polymer 2-1
2. Synthesis of Polymer 2
2-12 were synthesized.

[0122]

[Chemical 36]

[0123]

[Chemical 37]

[0124]

[Chemical 38]

[Example] The polymer compounds of the present invention were evaluated for resolution when blended in a resist material as a base resin. [Examples 1 to 12 and Comparative Examples 1 to 4] The polymers represented by the above formulas (Polymers 1 to 12) and the polymers represented by the following formulas for comparison (Polymers 13 to 16).
Was used as a base resin, and an acid generator, 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.

[0126]

[Chemical Formula 39]

The resist solution was applied to the antireflection film (A manufactured by Nissan Chemical Co., Ltd.
(RC25, 77 nm) was spin-coated on a silicon wafer and heat-treated at 130 ° C. for 60 seconds to form a resist film having a thickness of 375 nm. ArF excimer laser stepper (manufactured by Nikon, NA = 0.5)
5) exposure to 100 ° C, 110 ° C or 130 ° C
After heat treatment at 60 ° C. for 60 seconds, paddle development was performed for 60 seconds using a 2.38% tetramethylammonium hydroxide aqueous solution to form a 1: 1 line and space pattern. 0.20 μm of the cleaved developed wafer was observed with a cross-section SEM (scanning electron microscope).
The minimum line width (μm) of the separated line and space at the exposure amount (optimal exposure amount = Eop, mJ / cm ² ) that resolves the line and space of 1: 1 at 1: 1 was defined as the resolution of the evaluation resist. Further, the shape of the pattern at that time was classified into any of a rectangle, a rounded head, a T-top, a forward taper, and a reverse taper. Furthermore, as an evaluation of developer affinity,
The presence or absence of repelling of the developing solution on the wafer during paddle development was observed, and the results were represented by x and o respectively.

Table 1 shows the composition and evaluation result of each resist of the examples. Table 2 shows the composition and evaluation result of each resist of the comparative example. In addition, in Table 1 and Table 2, the acid generator, the basic compound, and the solvent are as follows. In addition, all the solvents are KH-20 (Asahi Glass Co., Ltd.) 0.0
The one containing 1% by weight was used. TPSNf: triphenylsulfonium nonafluorobutane sulfonate TMMEA: trismethoxymethoxyethylamine PGMEA: propylene glycol methyl ether acetate CyHO: cyclohexanone

[0129]

[Table 1]

[0130]

[Table 2]

From the results shown in Tables 1 and 2, it was confirmed that the resist material of the present invention was excellent in sensitivity, resolution, solvent solubility and developer affinity in ArF excimer laser exposure.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Sachi Hasegawa             28-1 Nishifukushima, Kubiki Village, Nakakubiki District, Niigata Prefecture             Shin-Etsu Chemical Co., Ltd.Research on new functional materials technology             In-house (72) Inventor Tsuyoshi Kinsei             28-1 Nishifukushima, Kubiki Village, Nakakubiki District, Niigata Prefecture             Shin-Etsu Chemical Co., Ltd.Research on new functional materials technology             In-house F-term (reference) 2H025 AA01 AA02 AA04 AA09 AA14                       AC08 AD03 BE00 BE10 BG00                       CB14 CB41 CB55 FA01 FA12                 4J100 AL08P AL08Q BA11Q BA15Q                       BC09P BC58Q CA03 CA04                       CA05 CA06 JA38

Claims (4)

[Claims] 1. A repeating unit represented by the following general formula (1) and an adamantane structure or tetracyclo [4.4.
0.1 ^2,5 . [ ^7,10 ] Dodecane structure-containing repeating unit having a carboxylic acid protected by an acid-decomposable protecting group.
500,000 polymer compounds. [Chemical 1] (In the formula, R ¹ represents a hydrogen atom or a methyl group. R ² represents a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms. R ³ represents a hydrogen atom or CO ₂ R. ⁴ shows the .R ⁴
Represents a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms. ) 2. An adamantane structure or tetracyclo [4.4.0.1 ^2,5 . The repeating unit having a carboxylic acid protected by an acid-decomposable protecting group containing a ^1,7,10 ] dodecane structure is any one or more of the units represented by the following general formulas (2) to (4). The polymer compound according to claim 1. [Chemical 2] (In the formula, R ⁵ , R ⁷ , and R ¹⁰ represent a hydrogen atom or a methyl group. R ⁶ , R ⁸ , R ⁹ , and R ¹¹ are linear groups having 1 to 15 carbon atoms,
A branched or cyclic alkyl group is shown. ) 3. A resist material containing the polymer compound according to claim 1 as a base resin. 4. A step of applying the resist material according to claim 3 onto a substrate, a step of exposing with a high energy beam or an electron beam through a photomask after heat treatment, and after heat treatment as necessary. And a step of developing with a developing solution.