JP2002308938A - Ether compound, polymer compound, resist material and pattern-forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resist material which comprises as a base resin a polymer compound and is sensitive to high energy rays, excellent in sensitivity, resolution and etching resistance and therefore suitable for use in microfabrication by electron rays or far ultraviolet rays. SOLUTION: An ether compound represented by formula (I) (wherein R<1> is hydrogen atom or a 1-6C linear, branched or cyclic alkyl group; R<2> is a 1-6C linear, branched or cyclic alkyl group; R<3> is hydrogen atom or a 1-15C aryl or alkoxycarbonyl group, and hydrogen atoms on the constituent carbon may be partially or totally replaced with a halogen atom; (k) is an integer of 0 or 1; (m) is an integer of 0-3; and (n) is an integer of 3-6) is provided. The resist material has low absorption particularly at an exposed wavelength of an ArF excimer laser or a KrF excimer laser and therefore can easily form a fine pattern perpendicular to a substrate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to (1) a specific ether compound, (2) a polymer compound containing a specific repeating unit, (3) a resist material containing the polymer compound as a base resin, and (4) The present invention relates to a pattern forming method using the resist material.

[0002]

2. Description of the Related Art In recent years, as the integration and speed of LSIs have become higher and higher, the pattern rules have been required to be finer. Among them, KrF excimer laser light, A
Photolithography using an rF excimer laser beam as a light source has long been desired to be realized as a technology indispensable for ultra-fine processing of 0.3 μm or less.

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

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

[0005]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above circumstances, and (1) an ether compound which gives a polymer compound having excellent substrate adhesion (2) reactivity, rigidity and substrate adhesion An excellent polymer compound, (3) a resist material using the polymer compound as a base resin and having resolution and etching resistance far higher than conventional products, and (4) a pattern forming method using the resist material. With the goal.

[0006]

Means for Solving the Problems and Embodiments of the Invention The present inventors have conducted intensive studies in order to achieve the above object, and as a result, a novel ether compound represented by the following general formula (1) obtained by the method described below. Is a raw material of a polymer compound having excellent substrate adhesion, and a novel polymer compound having a weight average molecular weight of 1,000 to 500,000 obtained using this compound is excellent in reactivity and rigidity. The resist material used as the base resin obtained using the compound has high resolution and high etching resistance,
They have found that this resist material is extremely effective for precise fine processing.

That is, the present invention provides the following ether compounds. [I] An ether compound represented by the following general formula (1).

Embedded image (In the formula, R ¹ is a hydrogen atom or a straight chain having 1 to 6 carbon atoms;
Shows a branched or cyclic alkyl group. R ² has 1 to 1 carbon atoms
6 represents a linear, branched or cyclic alkyl group. R ³
Represents a hydrogen atom, or an acyl group or an alkoxylcarbonyl group having 1 to 15 carbon atoms, and a part or all of the hydrogen atoms on the constituent carbons may be substituted with a halogen atom. k is 0 or 1, m is an integer of 0 to 3, and n is an integer of 3 to 6. )

Further, the present invention provides the following polymer compound. [II] It contains a repeating unit represented by the following general formula (1-1) or (1-2) starting from an ether compound represented by the general formula (1), and has a weight average molecular weight of 1,000.
A polymer compound having a molecular weight of up to 500,000.

Embedded image (In the formula, k, m, n, and R ^{1 to} R ³ have the same meanings as described above.)

[III] In addition to the repeating unit represented by the above general formula (1-1), the compound according to [II], further comprising a repeating unit represented by the following general formula (2-1): Molecular compound.

Embedded image(Where k is the same as above. R⁴Is a hydrogen atom,
Or CH₂CO₂R ⁶Is shown. R⁵Is a hydrogen atom,
Cyl group or CO₂R⁶Is shown. R⁶Has 1 to 15 carbon atoms
It represents a linear, branched or cyclic alkyl group. R⁷Is an acid
Shows an unstable group. R⁸Is halogen atom, hydroxyl group, carbon number
1 to 15 linear, branched or cyclic alkoxy groups,
A siloxy group or an alkylsulfonyloxy group, or
Is a linear, branched or cyclic alkoxy having 2 to 15 carbon atoms
Represents a cyclocarbonyloxy group or an alkoxyalkoxy group
And part or all of the hydrogen atoms on the constituent carbon atoms are halogenated
And it may be substituted by a nitrogen atom. Z is a single bond or carbon number
1-5 linear, branched or cyclic (p + 2) -valent carbonized
Represents a hydrogen group, and when it is a hydrocarbon group, one or more
Methylene is replaced by oxygen to form a chain or cyclic ether
Or two hydrogens on the same carbon are replaced by oxygen
To form a ketone. p is 0, 1 or 2
You. )

[IV] In addition to the repeating unit represented by the general formula (1-1), the following general formulas (2-1) and (3)
The polymer compound according to [II], which contains a repeating unit represented by the formula:

Embedded image(Where Z, k, p, R⁴~ R⁸Is the same as above.
Y is an oxygen atom, or NR ⁹And R⁹Has 1 to 6 carbon atoms
Represents a linear, branched or cyclic alkyl group. )

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

Embedded image (In the formula, Y, Z, k, p, and R ^{4 to} R ⁹ are the same as above.)

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

Embedded image (In the formula, Z, k, p, and R ^{4 to} R ⁸ are the same as described above.)

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

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

The ether compound of the general formula (1) has a high polarity because it has a hydroxyl group, an acyloxy group or an alkoxycarbonyloxy group in addition to the ether structure. Therefore, a polymer compound containing the repeating unit represented by (1-1) or (1-2) as a raw material of this compound achieves excellent substrate adhesion. In addition, these repeating units have a high rigidity because the main chain contains an alicyclic ring having a bridge. Furthermore, a carbon chain of an appropriate length introduced between the ether structure and the rigid main chain appropriately moderates the rigidity which was conventionally excessive, and the ether structure portion is located away from the main chain. As a result, it has become more effective as a polar group, and as a result, it has much higher substrate adhesion than conventional products. In addition, low reactivity, which was a bigger problem than in the past, was improved by increasing the diffusibility of generated acid by the effect of carbon chain introduction, and at the same time, reduction of line edge roughness was achieved. Therefore, a resist material using this polymer compound as a base resin has excellent performance in all of sensitivity, resolution and etching resistance, and is extremely useful for forming a fine pattern.

Hereinafter, the present invention will be described in more detail.
The ether compound of the present invention is represented by the following general formula (1).

Embedded image

Here, R ¹ is a hydrogen atom or a group having 1 to 1 carbon atoms.
6 represents a linear, branched or cyclic alkyl group, specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-
Examples thereof include butyl, tert-butyl, tert-amyl, n-pentyl, n-hexyl, cyclopentyl, cyclohexyl and the like. R ² represents a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, and specific examples thereof include those described above as specific examples of the alkyl group for R ¹ . R
³ represents a hydrogen atom or an acyl group or an alkoxylcarbonyl group having 1 to 15 carbon atoms, and a part or all of the hydrogen atoms on the constituent carbons may be substituted with a halogen atom. Specifically, formyl, acetyl, propionyl,
Examples include pivaloyl, methoxycarbonyl, ethoxycarbonyl, tert-butoxycarbonyl, trifluoroacetyl, trichloroacetyl, 3,3,3-trifluoropropionyl and the like. k is 0 or 1, m is 0
3, n is an integer of 3 to 6.

Specific examples of the ether compound of the present invention are shown below, but the invention is not limited thereto. In the following formula, Ac represents an acetyl group and t-Bu represents a tert-butyl group (the same applies hereinafter).

[0019]

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The production of the ether compound of the present invention can be carried out, for example, by the following steps, but is not limited thereto.

[0021]

Embedded image

[0022] ^{Here, k, m, n, R} 1 ~R 3 is the same as described above. X 'is a halogen atom. L is a hydroxyl group,
And a leaving group such as a halogen atom, an acyloxy group, an alkoxycarbonyloxy group, a p-nitrophenyloxy group.

Step A is a step in which a Grignard reagent is prepared with a halogenated ether (a) and magnesium, and a nucleophilic addition reaction is performed on the carbonyl compound (b) to obtain an alcohol (c). Although a Grignard reaction is mentioned here as a specific example of the nucleophilic addition reaction, this step is not limited to this. The reaction proceeds easily under known conditions. Preferably, the starting material halogenated ether (a), carbonyl compound (b), and magnesium are mixed in a solvent such as tetrahydrofuran or diethyl ether, and heated or heated as necessary. It is preferable to perform the cooling.

Step B is a step in which the corresponding acylated product or alkoxycarbonylated product (d) is obtained by esterifying the alcohol (c). Esterifying agent R
^{As 3} L, for example, carboxylic acids such as formic acid (L = OH
), Acid halides such as acetyl chloride, acetyl bromide, and propionyl chloride (when L = halogen atom), acetic anhydride, trifluoroacetic anhydride, formic acetic acid mixed acid anhydride, di-t-butyl dicarbonate, etc. Acid anhydrides (in the case of L = acyloxy group or alkoxycarbonyloxy group),
Activated esters such as p-nitrophenyl acetate and p-nitrophenyl propionate (where L is a leaving group such as p-nitrophenyloxy group) can be mentioned. Except when the esterifying agent is a carboxylic acid, it is desirable to use a base such as triethylamine, pyridine, or 4-dimethylaminopyridine. The reaction proceeds easily under known conditions, but preferably in the absence of a solvent or in a solvent such as tetrahydrofuran, diethyl ether, n-hexane or toluene, the starting material alcohol (c), esterifying agent R ³ L, In some cases, the above-described bases are mixed, and if necessary, heating or cooling may be performed.

The polymer compound of the present invention contains a repeating unit represented by the following general formula (1-1) or (1-2) starting from the ester compound represented by the general formula (1). Characteristic weight average molecular weight 1,000 ~
500,000.

[0026]

Embedded image In the formula, k, m, n, R ^{1 to} R ³ are the same as described above.

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

Embedded image(Where k is the same as above. R⁴Is a hydrogen atom,
Or CH₂CO₂R ⁶Is shown. R⁵Is a hydrogen atom,
Cyl group or CO₂R⁶Is shown. R⁶Has 1 to 15 carbon atoms
It represents a linear, branched or cyclic alkyl group. R⁷Is an acid
Shows an unstable group. R⁸Is halogen atom, hydroxyl group, carbon number
1 to 15 linear, branched or cyclic alkoxy groups,
A siloxy group or an alkylsulfonyloxy group, or
Is a linear, branched or cyclic alkoxy having 2 to 15 carbon atoms
Represents a cyclocarbonyloxy group or an alkoxyalkoxy group
And part or all of the hydrogen atoms on the constituent carbon atoms are halogenated
And it may be substituted by a nitrogen atom. Z is a single bond or carbon number
1-5 linear, branched or cyclic (p + 2) -valent carbonized
Represents a hydrogen group, and when it is a hydrocarbon group, one or more
Methylene is replaced by oxygen to form a chain or cyclic ether
Or two hydrogens on the same carbon are replaced by oxygen
To form a ketone. p is 0, 1 or 2
You. )

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

Embedded image(Where Z, k, p, R⁴~ R⁸Is the same as above.
Y is an oxygen atom, or NR ⁹And R⁹Has 1 to 6 carbon atoms
Represents a linear, branched or cyclic alkyl group. R⁹
Specifically, methyl, ethyl, n-propyl, i
Sopropyl, n-butyl, isobutyl, sec-butyl
Tert-butyl, tert-amyl, n-pliers
, N-hexyl, cyclopentyl, cyclohexyl, etc.
Can be exemplified. )

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

Embedded image (In the formula, Y, Z, k, p, and R ^{4 to} R ⁹ are the same as above.)

4. What contains the repeating unit represented by the following general formula (2-2) in addition to the repeating unit represented by the above general formula (1-2).

Embedded image (In the formula, Z, k, p, and R ^{4 to} R ⁸ are the same as described above.)

Here, R ⁴ is a hydrogen atom, a methyl group or C 4
H ₂ CO ₂ R ⁶ is shown. R ⁵ represents a hydrogen atom, a methyl group or CO ₂ R ⁶ . R ⁶ represents a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert. -Butyl group, ter
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, etc. it can. R ⁷ represents an acid labile group, and specific examples thereof will be described later. R ⁸ is a halogen atom, a hydroxyl group, a carbon number of 1 to 15
A linear, branched or cyclic alkoxy group, an acyloxy group, or an alkylsulfonyloxy group, or a linear, branched or cyclic alkoxycarbonyloxy group having 2 to 15 carbon atoms, an alkoxyalkoxy group, Some or all of the hydrogen atoms on the carbon atoms may be replaced by halogen atoms, specifically, fluorine, chlorine, bromine,
Methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert
-Butoxy, tert-amyloxy, n-pentoxy, n-hexyloxy, cyclopentyloxy, cyclohexyloxy, ethylcyclopentyloxy, butylcyclopentyloxy, ethylcyclohexyloxy, butylcyclohexyloxy, adamantyloxy Group, ethyl adamantyloxy group, butyl adamantyloxy group, formyloxy group, acetoxy group, ethylcarbonyloxy group, pivaloyloxy group, methoxycarbonyloxy group, ethoxycarbonyloxy group, tert-butoxycarbonyloxy group,
Methanesulfonyloxy group, ethanesulfonyloxy group, n-butanesulfonyloxy group, trifluoroacetoxy group, trichloroacetoxy group, 2,2,2-
Trifluoroethylcarbonyloxy group, methoxymethoxy group, 1-ethoxyethoxy group, 1-ethoxypropoxy group, 1-tert-butoxyethoxy group, 1-cyclohexyloxyethoxy group, 2-tetrahydrofuranyloxy group, 2-tetrahydropyranyl Oxy groups and the like can be exemplified. Z represents a single bond or a linear, branched or cyclic (p + 2) -valent hydrocarbon group having 1 to 5 carbon atoms, and in the case of a hydrocarbon group, at least one methylene is substituted with oxygen. To form a chain or cyclic ether, or two hydrogens on the same carbon may be replaced by oxygen to form a ketone. For example, when p = 0, specifically methylene,
Ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, 1,2-propanediyl, 1,
3-butanediyl, 1-oxo-2-oxapropane-
Examples thereof include 1,3-diyl and 3-methyl-1-oxo-2-oxabutane-1,4-diyl. When p = 0, p hydrogen atoms are excluded from the above specific examples ( p +
2) Valent groups and the like can be exemplified.

As the acid labile group for R ⁷ , various compounds can be used. Specifically, the following general formulas (L1) to (L)
Group represented by 4), having 4 to 20 carbon atoms, preferably 4 to 1 carbon atoms
5 tertiary alkyl groups, each alkyl group having 1 carbon atom
And an oxoalkyl group having 4 to 20 carbon atoms.

[0033]

Embedded image

Here, a chain line indicates a bond (hereinafter referred to as a bond).
Mr). Where R^L01, R^L02Is a hydrogen atom or carbon number
1-18, preferably 1-10, linear, branched or cyclic
Represents an alkyl group, specifically a methyl group, an ethyl group
Group, propyl group, isopropyl group, n-butyl group, se
c-butyl group, tert-butyl group, cyclopentyl
Group, cyclohexyl group, 2-ethylhexyl group, n-O
An example is a octyl group. R ^L03Has 1 to 18 carbon atoms,
It preferably has 1 to 10 hetero atoms such as oxygen atoms.
Represents a monovalent hydrocarbon group which may be linear, branched or cyclic.
Alkyl group, some of these hydrogen atoms are hydroxyl,
Lucoxy group, oxo group, amino group, alkylamino group, etc.
Can be mentioned, specifically,
And the like.

[0035]

Embedded image

R ^L01 and R ^L02 , R ^L01 and R ^L03 , and R ^L02 and R ^L03 may form a ring. When a ring is formed, R ^L01 , R ^L02 , R
^L03 has 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms.
Represents a linear or branched alkylene group.

^RL04 has 4 to 20 carbon atoms, preferably 4 carbon atoms.
A tertiary alkyl group having 1 to 15 carbon atoms, each alkyl group being a trialkylsilyl group having 1 to 6 carbon atoms, an oxoalkyl group having 4 to 20 carbon atoms or a group represented by the above formula (L1); As the 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) propane-2
-Yl group, 1-ethylcyclopentyl group, 1-butylcyclopentyl group, 1-ethylcyclohexyl group, 1-butylcyclohexyl group, 1-ethyl-2-cyclopentenyl group, 1-ethyl-2-cyclohexenyl group, 2- Examples thereof include a methyl-2-adamantyl group and a 2-ethyl-2-adamantyl group. Examples of the trialkylsilyl group include:
Specifically, a trimethylsilyl group, a triethylsilyl group,
Examples thereof include a dimethyl-tert-butylsilyl group, and specific examples of the oxoalkyl group include a 3-oxocyclohexyl group, a 4-methyl-2-oxooxan-4-yl group, and a 5-methyl-2-oxooxolane- group. Examples thereof include a 5-yl group. x is an integer of 0-6.

^RL05 represents a monovalent hydrocarbon group which may contain a heteroatom having 1 to 8 carbon atoms or an aryl group which may be substituted and has 6 to 20 carbon atoms. Specific examples of the hydrocarbon group include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, and ter
t-amyl group, n-pentyl group, n-hexyl group, cyclopentyl group, linear or branched or cyclic alkyl group such as cyclohexyl group, some of these hydrogen atoms are hydroxyl, alkoxy, carboxy, Examples thereof include those substituted with an alkoxycarbonyl group, an oxo group, an amino group, an alkylamino group, a cyano group, a mercapto group, an alkylthio group, a sulfo group, and the like.Specific examples of the optionally substituted aryl group include: Represents a phenyl group, a methylphenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group or the like. y is 0 or 1, z is 0, 1,
It is either 2, 3 or 2y + z = 2 or 3.

R^L06Contains a heteroatom having 1 to 8 carbon atoms.
Monovalent hydrocarbon group or C6-C20 substitution
Represents an optionally substituted aryl group, specifically R
^L05And the like can be exemplified. R^L07~ R
^L16Are each independently a hydrogen atom or a group having 1 to 15 carbon atoms.
A monovalent hydrocarbon group that may contain a heteroatom,
Physically, methyl, ethyl, propyl, isopropyl
Group, n-butyl group, sec-butyl group, tert-butyl group
Tyl group, tert-amyl group, n-pentyl group, n-he
Xyl group, n-octyl group, n-nonyl group, n-decyl
Group, cyclopentyl group, cyclohexyl group, cyclopen
Tylmethyl group, cyclopentylethyl group, cyclopentyl
Rubutyl group, cyclohexylmethyl group, cyclohexyl
Linear or branched such as ethyl group and cyclohexylbutyl group
Or a cyclic alkyl group, in which some of these hydrogen atoms are hydroxyl
Group, alkoxy group, carboxy group, alkoxy carbonyl
Group, oxo group, amino group, alkylamino group, cyano
Group, mercapto group, alkylthio group, sulfo group, etc.
Can be exemplified. R^L07~ R^L16Are each other
May form a ring (for example, R^L07And R
^L08, R^L07And R^L09, R ^L08And R^L10, R
^L09And R^L10, R^L11And R^L12, R^L13And R
^{L 14}Etc.), in which case a heteroatom having 1 to 15 carbon atoms
Represents a divalent hydrocarbon group which may contain
One hydrogen atom from those exemplified for the monovalent hydrocarbon group
Excluded ones can be exemplified. Also, R^L07~ R^L16
Are bonded to adjacent carbons without any intervention
To form a double bond (for example, R ^L07And R
^L09, R^L09And R^L15, R^L13And R
^L15etc).

The following groups can be specifically exemplified as linear or branched ones among the acid labile groups represented by the formula (L1).

[0041]

Embedded image

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

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

Specific examples of the acid labile group of the above formula (L3) include 1-methylcyclopentyl, 1-ethylcyclopentyl, 1-n-propylcyclopentyl, 1-isopropylcyclopentyl, 1-n-butylcyclopentyl, -Sec-butylcyclopentyl, 1-methylcyclohexyl, 1-ethylcyclohexyl, 3-methyl-1-cyclopenten-3-yl, 3-ethyl-1-cyclopenten-3-yl, 3-methyl-1-cyclohexene-3- Yl, 3-ethyl-1-cyclohexene-3
-Yl and the like.

Specific examples of the acid labile group of the formula (L4) include the following groups.

Embedded image

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

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

[0048]

Embedded image

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

[0050]

Embedded image

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

[0052]

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

[0054]

Embedded image

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

[0056]

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

[0058]

Embedded image (Wherein, R ⁰⁰¹ is a hydrogen atom, a methyl group or CH ₂ CO
₂ R ⁰⁰³ is shown. R ^{0 02} 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. R ⁰⁰⁴ represents a hydrogen atom or a monovalent hydrocarbon group having a carboxy group having 1 to 15 carbon atoms or a hydroxyl group. R ^{0 05} ~R
^{008 represents} a monovalent hydrocarbon group having a carboxy group or a hydroxyl group having 1 to 15 carbon atoms, and the rest are each independently a hydrogen atom or a linear, branched or cyclic group having 1 to 15 carbon atoms. Represents an alkyl group. R ^{005 to} R
⁰⁰⁸ may form a ring with each other, in which case at least one of R ^{005 to} R ⁰⁰⁸ has 1 to 15 carbon atoms.
A carboxy group or a divalent hydrocarbon group containing a hydroxyl group, and the rest are each independently a single bond or a carbon number of 1 to 1.
5 represents a linear, branched or cyclic alkylene group. R
⁰⁰⁹ represents a monovalent hydrocarbon group having a —CO ₂ — partial structure having 3 to 15 carbon atoms. At least one of R ^{010 to} R ^{013 represents} a monovalent hydrocarbon group having a —CO ₂ — partial structure having 2 to 15 carbon atoms, and the rest are each independently a hydrogen atom or a straight chain having 1 to 15 carbon atoms. A branched, branched or cyclic alkyl group. R ⁰¹⁰ to R ^013, taken together, may form a ring, in which case ^{R 0} 10 ^{to R 013}
At least one is -CO 2 C 1 -C 15 _- moiety represents a divalent hydrocarbon group containing, while the remaining are independently a single bond or a C15 straight, branched or Shows a cyclic alkylene group. R ⁰¹⁴ has 7 to 15 carbon atoms
Or a polycyclic hydrocarbon group or an alkyl group containing a polycyclic hydrocarbon group. R ⁰¹⁵ represents an acid labile group. X is C
Shows the H ₂ or an oxygen atom. k is 0 or 1. )

Here, R⁰⁰¹Is a hydrogen atom, a methyl group or
Is CH₂CO₂R⁰⁰³Is shown. R ⁰⁰³Examples of
Will be described later. R⁰⁰²Is a hydrogen atom, a methyl group or C
O₂R⁰⁰³Is shown. R⁰⁰³Is a linear chain having 1 to 15 carbon atoms
Represents a branched, branched or cyclic alkyl group.
Chill, ethyl, propyl, isopropyl, n-
Butyl group, sec-butyl group, tert-butyl group, t
ert-amyl group, n-pentyl group, n-hexyl group,
Cyclopentyl group, cyclohexyl group, ethylcyclope
Ethyl group, butylcyclopentyl group, ethylcyclohexyl
Silyl group, butylcyclohexyl group, adamantyl group, d
Tiladamantyl group, butyladamantyl group and the like are exemplified.
Wear. R⁰⁰⁴Is a hydrogen atom or a carbohydrate having 1 to 15 carbon atoms
A monovalent hydrocarbon group containing a xy group or a hydroxyl group,
Specifically, carboxyethyl, carboxybutyl, cal
Boxycyclopentyl, carboxycyclohexyl, mosquito
Ruboxinorbornyl, carboxyadamantyl, hydr
Roxyethyl, hydroxybutyl, hydroxycyclope
Methyl, hydroxycyclohexyl, hydroxynorbo
Lunyl, hydroxyadamantyl and the like can be exemplified. R
⁰⁰⁵~ R⁰⁰⁸At least one of which has 1 to 15 carbon atoms
A monovalent hydrocarbon group containing a carboxy group or a hydroxyl group
And the rest are each independently a hydrogen atom or a carbon number of 1 to 1.
5 represents a linear, branched or cyclic alkyl group. carbon
Monovalent containing a carboxy group or a hydroxyl group of Formulas 1 to 15
Specific examples of the hydrocarbon group include carboxy and carboxy.
Cimethyl, carboxyethyl, carboxybutyl, hydr
Roxymethyl, hydroxyethyl, hydroxybutyl,
2-carboxyethoxycarbonyl, 4-carboxybut
Toxycarbonyl, 2-hydroxyethoxycarboni
, 4-hydroxybutoxycarbonyl, carboxy
Clopentyloxycarbonyl, carboxycyclohexyl
Siloxycarbonyl, carboxynorbornyloxy
Carbonyl, carboxyadamantyloxycarboni
, Hydroxycyclopentyloxycarbonyl, hydr
Roxycyclohexyloxycarbonyl, hydroxyno
Rubornyloxycarbonyl, hydroxyadamantyl
Oxycarbonyl and the like can be exemplified. C1-15 straight
As the chain, branched, or cyclic alkyl group, specifically,
R⁰⁰³The same thing as what was illustrated by can be illustrated. R
⁰⁰⁵~ R⁰⁰⁸May form a ring with each other,
In the case of R⁰⁰⁵~ R⁰⁰⁸At least one of is carbon
Divalent containing a carboxy group or a hydroxyl group of Formulas 1 to 15
Represents a hydrocarbon group, and the rest are each independently a single bond or a carbon
A linear, branched or cyclic alkylene group having a prime number of 1 to 15
Is shown. It contains a carboxy group or a hydroxyl group having 1 to 15 carbon atoms.
Specific examples of the divalent hydrocarbon group having
Exemplified by a monovalent hydrocarbon group containing a boxy group or a hydroxyl group
Can be exemplified by removing one hydrogen atom from the
You. Linear, branched, or cyclic alkylene having 1 to 15 carbon atoms
Specific examples of the R group include R⁰⁰³From the example illustrated in
One in which one hydrogen atom has been removed can be exemplified.

R ⁰⁰⁹ represents a monovalent hydrocarbon group having a —CO ₂ — partial structure having 3 to 15 carbon atoms, and specifically, 2-oxooxolan-3-yl and 4,4-dimethyl-
2-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 Can be exemplified. R ^{010 to} R ⁰¹³
At least one is -CO 2 of 2 to 15 carbon atoms _- a monovalent hydrocarbon group containing a partial structure, while the remaining R's are independently hydrogen or C15 straight, branched or Shows a cyclic alkyl group. -CO ₂ having 2 to 15 carbon atoms
-Specific examples of the monovalent hydrocarbon group having a partial structure include 2-oxooxolan-3-yloxycarbonyl, 4,4-dimethyl-2-oxooxolan-3-yloxycarbonyl, -Methyl-2-oxooxan-4-yloxycarbonyl, 2-oxo-1,3-dioxolan-4-ylmethyloxycarbonyl, 5-methyl-2-oxooxolan-5-yloxycarbonyl and the like can be exemplified. C1-C15 linear, branched,
Specific examples of the cyclic alkyl group include the same as those exemplified for R ⁰⁰³ . R ^{010 to} R
⁰¹³ may form a ring with each other, in which case at least one of R ^{010 to} R ⁰¹³ has 1 to 15 carbon atoms.
Represents a divalent hydrocarbon group having a —CO ₂ — partial structure, and the rest each independently represent a single bond or a linear, branched, or cyclic alkylene group having 1 to 15 carbon atoms. Carbon number 1
15 of -CO ₂ - Examples of the divalent hydrocarbon group containing a partial structure include 1-oxo-2-oxa-1,3-diyl, 1,3-dioxo-2-oxa-propane 1,3-diyl, 1-oxo-2-Okisabutan-1,4-diyl, other like 1,3-dioxo-2-Okisabutan-1,4-diyl, the -CO ₂ - containing partial structure Examples thereof include those obtained by removing one hydrogen atom from those exemplified for the monovalent hydrocarbon group. Specific examples of the linear, branched, or cyclic alkylene group having 1 to 15 carbon atoms include those exemplified in ^R003 except for removing one hydrogen atom.

R ⁰¹⁴ represents a polycyclic hydrocarbon group having 7 to 15 carbon atoms or an alkyl group containing a polycyclic hydrocarbon group, and specifically, norbornyl, bicyclo [3.3.1]
Nonyl, tricyclo [5.2.1.0 ^2,6 ] decyl,
Adamantyl, ethyl adamantyl, butyl adamantyl, norbornylmethyl, adamantylmethyl and the like can be exemplified. R ⁰¹⁵ represents an acid labile group, and specific examples thereof include the same as those described in the above description. X is C
Shows the H ₂ or an oxygen atom. k is 0 or 1.

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

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

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

[0065]

Embedded image (In the formula, Y, Z, k, p, m, n, R ^{1 to} R ⁹ are the same as described above.)

[0066]

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

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

In this case, the polymer compound of the present invention comprises: (i) a monomer of the above formula (1a); (ii) a monomer of the above formulas (2a) to (4a); and (iii) a monomer of the above formula (M1a). To (M8a), and (iv) a monomer containing a carbon-carbon double bond other than (i) to (iii) above, for example, methyl methacrylate,
Substituted acrylates such as methyl crotonate, dimethyl maleate and dimethyl itaconate; unsaturated carboxylic acids such as maleic acid, fumaric acid and itaconic acid; substituted norbornenes such as norbornene and methyl norbornene-5-carboxylate; anhydrous Unsaturated acid anhydrides such as itaconic acid and other monomers may be copolymerized.

In the polymer compound of the present invention, a preferable content ratio of each repeating unit based on each monomer can be, for example, in the following range, but is not limited thereto. In addition, all% here are mol%
It is. (I) When the polymer compound contains a repeating unit represented by the general formula (1-1) and a repeating unit represented by (2-1), the monomer represented by the formula (1a) 1 to 90%, preferably 5 to 80%, more preferably 10 to 70% of a repeating unit represented by the formula (1-1) based on the formula (2-1) based on the monomer of the formula (2a) 1 to 90%, preferably 5 to 80%, more preferably 10 to 70% of the repeating unit represented by the formula (M5a) to (M8a)
-1) to (M8-1) represented by 0 to 5
0%, preferably 0-40%, more preferably 0-30
%, A repeating unit based on another monomer is 0 to 50%,
Preferably, it can contain 0 to 40%, more preferably 0 to 30%, respectively.

(II) The polymer compound represented by the general formula (1)
In the case of containing a repeating unit represented by -1), a repeating unit represented by (2-1) and a repeating unit represented by (3), a compound represented by the formula (1a) 1 to 49%, preferably 3 to 45%, more preferably 5 to 40% of the repeating unit represented by 1-1), and the repeating unit represented by the formula (2-1) based on the monomer of the formula (2a) A unit is 1 to 49%, preferably 3 to 45%, more preferably 5 to 40%; a repeating unit represented by the formula (3) based on the monomer of the formula (3a) is 50%; a formula (M5a) to Formula (M5) based on the monomer of (M8a)
-1) to 0 to 2 (M8-1).
5%, preferably 0-20%, more preferably 0-15
%, A repeating unit based on another monomer is 0 to 25%,
Preferably, it can contain 0 to 20%, more preferably 0 to 15%, respectively.

(III) The polymer compound comprises a repeating unit represented by the above general formula (1-1), a repeating unit represented by the above (2-1) and / or a repeating unit represented by the above (4) and (3) In the case of containing a repeating unit represented by the formula, the repeating unit represented by the formula (1-1) based on the monomer of the formula (1a) is 1 to 49%, preferably 3 to 45%, 5 to 40%, preferably 0 to 40%, preferably 0 to 35%, more preferably 0 to 30% of the repeating unit represented by the formula (2-1) based on the monomer of the formula (2a); 1 to 80%, preferably 1 to 70%, more preferably 1 to 50% of the repeating unit represented by the formula (4) based on the monomer of the formula (3a); 1 to 49%, preferably 5 to 45% of the repeating unit represented by (3) And more preferably 10 to 40% of the formula (M) based on the monomers of the formulas (M1a) to (M8a).
1) to a repeating unit represented by (M8-1) of 0 to 25
%, Preferably 0 to 20%, more preferably 0 to 15%
%, A repeating unit based on another monomer is 0 to 25%,
Preferably, it can contain 0 to 20%, more preferably 0 to 15%, respectively.

(IV) The polymer compound represented by the general formula (1)
In the case of containing a repeating unit represented by -2) and a repeating unit represented by (2-2), a repeating unit represented by the formula (1-2) based on the monomer of the formula (1a) 1 to 90%, preferably 5 to 80%, more preferably 10 to 70%, 1 to 90%, preferably 1 to 90% of the repeating unit represented by the formula (2-2) based on the monomer of the formula (2a) 5 to 80%, more preferably 10 to 70%, of the formula (M5) based on the monomers of formulas (M5a) to (M8a)
-2) to 0 to 5 of the repeating unit represented by (M8-2).
0%, preferably 0-40%, more preferably 0-30
%, A repeating unit based on another monomer is 0 to 50%,
Preferably, it can contain 0 to 40%, more preferably 0 to 30%, respectively.

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

The reaction conditions for the radical polymerization reaction are as follows: (a) A solvent such as a hydrocarbon such as benzene, an ether such as tetrahydrofuran, an alcohol such as ethanol, or a ketone such as methyl isobutyl ketone; An azo compound such as 2,2'-azobisisobutyronitrile or a peroxide such as benzoyl peroxide or lauroyl peroxide is used as an initiator.
(D) The reaction time is 0.5 to 48 hours.
It is preferable to set the time to about the time, but it is not excluded that the time is out of this range.

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

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

The polymer compound of the present invention is effective as a base polymer of a resist material, and the present invention provides a resist material containing the polymer compound.

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

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

[0080]

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

The above R ^101a , R ^101b , R ^101c
May be the same or different from each other, and specifically, as an alkyl group, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group , Hexyl group, heptyl group, octyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclopropylmethyl group,
Examples include a 4-methylcyclohexyl group, a cyclohexylmethyl group, a norbornyl group, and 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, a 2-oxocyclohexyl group, and the like. A 2-oxopropyl group, a 2-cyclopentyl-2-oxoethyl group, a 2-cyclohexyl-2-oxoethyl group, a 2- (4 -Methylcyclohexyl) -2-
An oxoethyl group and the like can be mentioned. Examples of the aryl group include a phenyl group, a naphthyl group, a p-methoxyphenyl group, an m-methoxyphenyl group, an o-methoxyphenyl group, an ethoxyphenyl group, a p-tert-butoxyphenyl group, and an m-tert-butoxyphenyl group. Alkylphenyl groups such as alkoxyphenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, ethylphenyl group, 4-tert-butylphenyl group, 4-butylphenyl group and dimethylphenyl group ,
Alkylnaphthyl groups such as methylnaphthyl group and ethylnaphthyl group, alkoxynaphthyl groups such as methoxynaphthyl group and ethoxynaphthyl group, dialkylnaphthyl groups such as dimethylnaphthyl group and diethylnaphthyl group, dimethoxynaphthyl groups and diethoxynaphthyl groups such as diethoxynaphthyl groups And alkoxynaphthyl groups. Examples of the aralkyl group include a benzyl group, a phenylethyl group, a phenethyl group and the like.
As the aryloxoalkyl group, 2-phenyl-2
And 2-aryl-2-oxoethyl groups such as -oxoethyl group, 2- (1-naphthyl) -2-oxoethyl group and 2- (2-naphthyl) -2-oxoethyl group. The non-nucleophilic counter ion of K ⁻ is chloride ion,
Halide ion such as bromide ion, triflate, 1,
Fluoroalkylsulfonates such as 1,1-trifluoroethanesulfonate and nonafluorobutanesulfonate; arylsulfonates such as tosylate, benzenesulfonate, 4-fluorobenzenesulfonate, 1,2,3,4,5-pentafluorobenzenesulfonate, and mesylate And alkyl sulfonates such as butane sulfonate.

[0082]

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

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

[0084]

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

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

[0086]

Embedded image (Wherein, R ¹⁰⁷ , R ¹⁰⁸ and R ^{109 each} have 1 to 1 carbon atoms.
2 represents a linear, branched or cyclic alkyl group or halogenated alkyl group, an aryl group or halogenated aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms. R ^{108, R 109} may be bonded to each other to form a cyclic structure, when they form a ^{ring, R 108,}
R ¹⁰⁹ represents a linear or branched alkylene group having 1 to 6 carbon atoms. )

The alkyl group, halogenated alkyl group, aryl group, halogenated aryl group and aralkyl group represented by R ¹⁰⁷ , R ¹⁰⁸ and R ¹⁰⁹ are R ¹⁰⁵ , R ¹⁰⁶
And the same groups as described in the above. Note that R
^As the alkylene group for ¹⁰⁸ and R ^109, a methylene group,
Examples include an ethylene group, a propylene group, a butylene group, and a hexylene group.

[0088]

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

[0089]

Embedded image (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 a part or all of the hydrogen atoms of these groups further have carbon atoms. R ¹¹¹ may be substituted with a linear or branched alkyl or alkoxy group, a nitro group, an acetyl group, or a phenyl group having from 1 to 4. R ¹¹¹ has 1 to 8 carbon atoms. Or a substituted alkyl group, alkenyl group or alkoxyalkyl group, phenyl group or naphthyl group, and a part or all of the hydrogen atoms of these groups are further an alkyl group or alkoxy group having 1 to 4 carbon atoms; ~ 4
A phenyl group optionally substituted by an alkyl group, an alkoxy group, a nitro group or an acetyl group; a heteroaromatic group having 3 to 5 carbon atoms; or a chlorine atom or a fluorine atom. )

Here, the arylene group of R ¹¹⁰ is 1,2-phenylene group, 1,8-naphthylene group or the like, and the alkylene group is methylene group, 1,2-ethylene group, 1,3-propylene group. Group, 1,4-butylene group,
1-phenyl-1,2-ethylene group, norbornane-
When the 2,3-diyl group or the like is an alkenylene group,
2-vinylene group, 1-phenyl-1,2-vinylene group,
5-norbornene-2,3-diyl group and the like.
As the alkyl group for R ¹¹¹ , R ^{101a to} R ^{10
The same} alkenyl groups as those described in ^{1c except} for a vinyl group, a 1-propenyl group, an allyl group, a 1-butenyl group,
-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, Examples of the alkoxyalkyl group include a methoxymethyl group, an ethoxymethyl group,
Propoxymethyl group, butoxymethyl group, pentoxylmethyl group, hexyloxymethyl group, heptyloxymethyl group, methoxyethyl group, ethoxyethyl group, propoxyethyl group, butoxyethyl group, pentoxyloxy group,
Hexyloxyethyl group, methoxypropyl group, ethoxypropyl group, propoxypropyl group, butoxypropyl group, methoxybutyl group, ethoxybutyl group, propoxybutyl group, methoxypentyl group, ethoxypentyl group,
Examples include a methoxyhexyl group and a methoxyheptyl group.

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

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

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

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

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

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

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

[0098]

Embedded image (Wherein, R ⁰⁰¹ is a hydrogen atom, a methyl group or CH ₂ CO
₂ R ⁰⁰³ is shown. R ^{0 02} 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. R ⁰⁰⁴ represents a hydrogen atom or a monovalent hydrocarbon group having a carboxy group having 1 to 15 carbon atoms or a hydroxyl group. R ^{0 05} ~R
^{008 represents} a monovalent hydrocarbon group having a carboxy group or a hydroxyl group having 1 to 15 carbon atoms, and the rest are each independently a hydrogen atom or a linear, branched or cyclic group having 1 to 15 carbon atoms. Represents an alkyl group. R ^{005 to} R
⁰⁰⁸ may form a ring with each other, in which case at least one of R ^{005 to} R ⁰⁰⁸ has 1 to 15 carbon atoms.
A carboxy group or a divalent hydrocarbon group containing a hydroxyl group, and the rest are each independently a single bond or a carbon number of 1 to 1.
5 represents a linear, branched or cyclic alkylene group. R
⁰⁰⁹ represents a monovalent hydrocarbon group having a —CO ₂ — partial structure having 3 to 15 carbon atoms. At least one of R ^{010 to} R ^{013 represents} a monovalent hydrocarbon group having a —CO ₂ — partial structure having 2 to 15 carbon atoms, and the rest are each independently a hydrogen atom or a straight chain having 1 to 15 carbon atoms. A branched, branched or cyclic alkyl group. R ⁰¹⁰ to R ^013, taken together, may form a ring, in which case ^{R 0} 10 ^{to R 013}
At least one is -CO 2 C 1 -C 15 _- moiety represents a divalent hydrocarbon group containing, while the remaining are independently a single bond or a C15 straight, branched or Shows a cyclic alkylene group. R ⁰¹⁴ has 7 to 15 carbon atoms
Or 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 represents CH ₂ or an oxygen atom. Y represents an oxygen atom, or ^{NR 018, R 018} is a straight, branched or cyclic alkyl group having 1 to 6 carbon atoms. k is 0 or 1
It is. a1 ', a2', a3 ', b1', b2 ', b
3 ′, c1 ′, c2 ′, c3 ′, d1 ′, d2 ′, d
3 ′ and e ′ are numbers from 0 to less than 1, and a1 ′ + a2 ′
+ A3 '+ b1' + b2 '+ b3' + c1 '+ c2' +
It satisfies c3 ′ + d1 ′ + d2 ′ + d3 ′ + e ′ = 1. f ', g', h ', i', j 'are numbers from 0 to less than 1, and satisfy f' + g '+ h' + i '+ j' = 1. Note that specific examples of each group are the same as those described above.

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

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

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

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

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

[0104]

Embedded image(Where R²⁰¹, R²⁰²Is a hydrogen atom,
Or a linear or branched alkyl group having 1 to 8 carbon atoms or
Shows an alkenyl group. R²⁰³Is a hydrogen atom or carbon number
1-8 linear or branched alkyl or alkenyl
Group or-(R ²⁰⁷)_hIndicates COOH. R²⁰⁴
Is-(CH₂)_i-(I = 2 to 10), carbon number 6 to 10
Arylene, carbonyl, sulfonyl, oxygen
Represents a hydrogen atom or a sulfur atom. R²⁰⁵Is a group having 1 to 10 carbon atoms.
Alkylene group, arylene group having 6 to 10 carbon atoms, carbonyl
A sulfonyl group, an oxygen atom or a sulfur atom. R
^{20 6}Is a hydrogen atom, a linear or branched C1-C8
Substituted with alkyl group, alkenyl group or each hydroxyl group
Phenyl group or naphthyl group. R²⁰⁷Is charcoal
Represents a linear or branched alkylene group having a prime number of 1 to 10
You. R²⁰⁸Represents a hydrogen atom or a hydroxyl group. j is 0-5
Is an integer. u and h are 0 or 1. s, t,
s ', t', s ", and t" are each s + t = 8,
s ′ + t ′ = 5, s ″ + t ″ = 4, and
To have at least one hydroxyl group in the phenyl skeleton
It is a number. α is a molecule of the compound of formulas (D8) and (D9)
It is a number that makes the amount 100 to 1,000. )

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

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

[0107]

Embedded image(Where R^L01, R^L02Is a hydrogen atom or carbon number 1
It represents 18 linear, branched or cyclic alkyl groups. R
^L03Has a heteroatom such as an oxygen atom having 1 to 18 carbon atoms.
And a monovalent hydrocarbon group which may be used. R^L01And R
^L02, R^L01And R ^L03, R^L02And R^L03What is
A ring may be formed, and when a ring is formed, R ^L01,
R^L02, R^L03Is a linear group having 1 to 18 carbon atoms
Or a branched alkylene group. R^L04Is carbon number 4
-20 tertiary alkyl groups, each alkyl group being carbon
A trialkylsilyl group having 1 to 6 carbon atoms,
A xoalkyl group or a group represented by the above general formula (L1)
Show. R^L05May contain a heteroatom having 1 to 8 carbon atoms
Good monovalent hydrocarbon group or substituted with 6 to 20 carbon atoms
Represents an optionally substituted aryl group. R^L06Represents 1 to 8 carbon atoms
A monovalent hydrocarbon group or carbon optionally containing a heteroatom
And represents an aryl group which may be substituted and has the number of 6 to 20.
R^L07~ R^L16Are each independently a hydrogen atom or carbon
Monovalent hydrocarbon optionally containing heteroatoms of formulas 1 to 15
Represents a group. R^L07~ R^L16Form a ring with each other
In that case, a heteroatom having 1 to 15 carbon atoms
It indicates a divalent hydrocarbon group that may be contained. Also, R^L07
~ R^L16Is a bond between adjacent carbons
Alternatively, they may combine to form a double bond. x is 0-6
Is an integer. y is 0 or 1, z is 0, 1, 2, 3
2y + z = 2 or 3
You. Note that specific examples of each group are the same as those described above.
It is like.

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

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

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

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

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

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

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

Further, one or more kinds of basic compounds represented by the following general formula (B) -1 can be added. N (X) _n (Y) _3-n (B) -1 wherein n = 1, 2 or 3. The side chains X may be the same or different and can be represented by the following general formulas (X) -1 to (X) -3. The side chain Y is the same or different and represents a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and may include an ether group or a hydroxyl group. Further, Xs may be bonded to each other to form a ring.

[0116] ^{wherein R 300, R 302, R 305} are independently straight or branched alkylene group of 1 to 4 carbon atoms,
R ³⁰¹ and R ³⁰⁴ are a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and may include one or more hydroxy groups, ether groups, ester groups, and lactone rings.

R ³⁰³ is a single bond or a linear or branched alkylene group having 1 to 4 carbon atoms, and R ³⁰⁶ is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. , A hydroxy group, an ether group, an ester group, or a lactone ring.

[0118]

Embedded image

The compound represented by formula (B) -1 is specifically exemplified below. Tris (2-methoxymethoxyethyl) amine, 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 [8.8.88] hexacosan, 4,7,13,18-tetraoxa-1,10-
Diazabicyclo [8.5.5] eicosan, 1,4,1
0,13-tetraoxa-7,16-diazabicyclooctadecane, 1-aza-12-crown-4, 1-aza-15-crown-5, 1-aza-18-crown-
6, tris (2-formyloxyethyl) amine, tris (2-formyloxyethyl) amine, tris (2
-Acetoxyethyl) amine, tris (2-propionyloxyethyl) amine, tris (2-butyryloxyethyl) amine, tris (2-isobutyryloxyethyl) amine, tris (2-valeryloxyethyl) amine, Tris (2-pivaloyloxyxyethyl) amine, N, N-bis (2-acetoxyethyl) 2- (acetoxyacetoxy) ethylamine, tris (2-methoxycarbonyloxyethyl) amine, tris (2-te
rt-butoxycarbonyloxyethyl) amine, tris [2- (2-oxopropoxy) ethyl] amine, tris [2- (methoxycarbonylmethyl) oxyethyl] amine, tris [2- (tert-butoxycarbonylmethyloxy) ethyl] Amine, tris [2- (cyclohexyloxycarbonylmethyloxy) ethyl]
Amine, tris (2-methoxycarbonylethyl) amine, tris (2-ethoxycarbonylethyl) amine,
N, N-bis (2-hydroxyethyl) 2- (methoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (methoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2 -(Ethoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (ethoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2- (2
-Methoxyethoxycarbonyl) ethylamine, N, N
-Bis (2-acetoxyethyl) 2- (2-methoxyethoxycarbonyl) ethylamine, N, N-bis (2-
(Hydroxyethyl) 2- (2-hydroxyethoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (2-acetoxyethoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2
-[(Methoxycarbonyl) methoxycarbonyl] ethylamine, N, N-bis (2-acetoxyethyl) 2-
[(Methoxycarbonyl) methoxycarbonyl] ethylamine, N, N-bis (2-hydroxyethyl) 2-
(2-oxopropoxycarbonyl) ethylamine,
N, N-bis (2-acetoxyethyl) 2- (2-oxopropoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2- (tetrahydrofurfuryloxycarbonyl) ethylamine, N, N-bis ( 2
-Acetoxyethyl) 2- (tetrahydrofurfuryloxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2-[(2-oxotetrahydrofuran-3-yl) oxycarbonyl] ethylamine, N,
N-bis (2-acetoxyethyl) 2-[(2-oxotetrahydrofuran-3-yl) oxycarbonyl] ethylamine, N, N-bis (2-hydroxyethyl) 2
-(4-hydroxybutoxycarbonyl) ethylamine, N, N-bis (2-formyloxyethyl) 2-
(4-formyloxybutoxycarbonyl) ethylamine, N, N-bis (2-formyloxyethyl) 2-
(2-formyloxyethoxycarbonyl) ethylamine, N, N-bis (2-methoxyethyl) 2- (methoxycarbonyl) ethylamine, N- (2-hydroxyethyl) bis [2- (methoxycarbonyl) ethyl] amine, N -(2-acetoxyethyl) bis [2- (methoxycarbonyl) ethyl] amine, N- (2-hydroxyethyl) bis [2- (ethoxycarbonyl) ethyl] amine, N- (2-acetoxyethyl) bis [2 -(Ethoxycarbonyl) ethyl] amine, N- (3-hydroxy-1-propyl) bis [2- (methoxycarbonyl)
Ethyl] amine, N- (3-acetoxy-1-propyl) bis [2- (methoxycarbonyl) ethyl] amine, N- (2-methoxyethyl) bis [2- (methoxycarbonyl) ethyl] amine, N-butylbis [2-
(Methoxycarbonyl) ethyl] amine, N-butylbis [2- (2-methoxyethoxycarbonyl) ethyl]
Amine, N-methylbis (2-acetoxyethyl) amine, N-ethylbis (2-acetoxyethyl) amine,
N-methylbis (2-pivaloyloxyxyethyl) amine, N-ethylbis [2- (methoxycarbonyloxy) ethyl] amine, N-ethylbis [2- (tert
-Butoxycarbonyloxy) ethyl] amine, tris (methoxycarbonylmethyl) amine, tris (ethoxycarbonylmethyl) amine, N-butylbis (methoxycarbonylmethyl) amine, N-hexylbis (methoxycarbonylmethyl) amine, β- (diethylamino) Examples thereof include, but are not limited to, -δ-valerolactone.

The amount of the basic compound to be compounded is as follows:
0.001 to 10 parts, preferably 0.01 to 10 parts by weight
One copy. If the amount is less than 0.001 part, the effect as an additive may not be sufficiently obtained, and if it exceeds 10 parts, the resolution and sensitivity may be reduced.

Further, a compound having a group represented by ΔC—COOH in the molecule can be blended in the resist composition of the present invention.

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

[0123]

Embedded image(Where R⁴⁰⁸Represents a hydrogen atom or a methyl group.
R⁴⁰², R⁴⁰³Is a hydrogen atom or carbon number 1
8 linear or branched alkyl or alkenyl groups
Show. R⁴⁰⁴Is a hydrogen atom or a straight chain having 1 to 8 carbon atoms or
Is a branched alkyl or alkenyl group, or-(R
⁴⁰⁹)_h-COOR 'group (R' is a hydrogen atom or -R
⁴⁰⁹-COOH). R⁴⁰⁵Is-(CH₂)_i
-(I = 2 to 10), an arylene group having 6 to 10 carbon atoms,
A carbonyl group, a sulfonyl group, an oxygen atom or a sulfur atom
Show. R⁴⁰⁶Is an alkylene group having 1 to 10 carbon atoms,
Arylene group, carbonyl group, sulfonyl of the number 6 to 10
Represents a group, an oxygen atom or a sulfur atom. R⁴⁰⁷Is a hydrogen atom
Or a linear or branched alkyl group having 1 to 8 carbon atoms,
A alkenyl group, a phenyl group each substituted with a hydroxyl group or
Represents a naphthyl group. R ⁴⁰⁹Is a linear chain having 1 to 10 carbon atoms
It represents a branched or branched alkylene group. R⁴¹⁰Is hydrogen field
A linear or branched alkyl group having 1 to 8 carbon atoms or
Is an alkenyl group or -R⁴¹¹-COOH group is shown. R
⁴¹¹Is a linear or branched alkylene having 1 to 10 carbon atoms
Shows a substituent group. j is an integer of 0-5. u and h are 0 or
It is one. s1, t1, s2, t2, s3, t3, s
4 and t4 are respectively s1 + t1 = 8, s2 + t2 = 5,
s3 + t3 = 4, s4 + t4 = 6, and
A number having at least one hydroxyl group in the phenyl skeleton
It is. κ represents the compound of the formula (A6) having a weight average molecular weight of 1,
The number is 000 to 5,000. λ is the value of equation (A7)
The compound has a weight average molecular weight of 1,000 to 10,000.
Number. )

[0124]

Embedded image (R ⁴⁰² , R ⁴⁰³ and R ⁴¹¹ have the same meaning as described above. R ⁴¹² represents a hydrogen atom or a hydroxyl group. S5, t
5 is a number satisfying s5 + t5 = 5, where s5 ≧ 0 and t5 ≧ 0. h ′ is 0 or 1. )

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

[0126]

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

[0127]

Embedded image

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

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

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

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

[0132]

Embedded image (Wherein R ⁵⁰¹ , R ⁵⁰² , R ⁵⁰³ , R ⁵⁰⁴ , R
⁵⁰⁵ are each a hydrogen atom, or a 1-8C straight, a branched or cyclic alkyl group, X, Y is 0 or a positive number, satisfying the following values. 0 ≦ X ≦ 30, 0 ≦
Y ≦ 30 and 0 ≦ X + Y ≦ 40. )

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

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

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

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

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

[0138]

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

[0139]

EXAMPLES The present invention will be specifically described below with reference to Synthesis Examples and Examples, but the present invention is not limited to the following Examples.

[Synthesis Example] The ether compound of the present invention and a polymer compound using the same as a raw material were synthesized according to the following formulation.

[Synthesis Example 1-1] 5- (1-hydroxy-
5-methoxypentyl) -2-norbornene (Mono)
Synthesis of mer1) 122.6 g of 1-chloro-4-methoxybutane was added to 30
It was dissolved in 0 g of tetrahydrofuran. This solution is
The solution was added dropwise to 4.3 g of metallic magnesium at 60 ° C. or lower over 2 hours. After stirring for 2 hours at room temperature, 122.2
g of 5-norbornene-2-carbaldehyde was added dropwise at 50 ° C. or lower over 1 hour. After stirring for 1 hour at room temperature to complete the reaction, 300 g of water and 44 g of 20% H
Cl was added and stirred. The mixture was extracted with 500 g of hexane, and the obtained organic layer was washed with water, dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure. The obtained oily substance was distilled under reduced pressure, and
58.6 g of 5- (1-hydroxy-5-methoxypentyl) -2-norbornene were obtained. The yield was 75.4%. IR (thin film): ν = 3415 (br.), 3057, 2
937, 2866, 1458, 1450, 1389, 1
120,719 cm ^-1 5- (1-hydroxy-5-methoxypentyl) -2-
Of norbornene (exo body: endo body = 45: 55)
¹ H-NMR (300 MHz in CDCl ₃ ): δ
= 0.46-0.52 (0.55H, ddd, J = 1
1.6, 4.7, 2.5 Hz), 0.88-0.94
(0.45H, ddd, J = 11.6, 4.1, 2.5
Hz), 1.9-1.67 (9H, m), 1.70-
1.78 (0.55H, ddd, J = 11.6, 9.
4,3.9 Hz), 1.81-1.89 (0.45H,
ddd, J = 11.6, 8.8, 3.9 Hz), 1.9
6-2.09 (1H, m), 2.76-3.04 (3
H, m), 3.30-3.41 (5H, m) (3.30
(Including 1.65H, s), 3.31 (1.35H, s)), 5.85-5.88 (0.45H, m), 5.9
7-6.00 (0.55H, m), 6.01-6.15
(1H, m).

[Synthesis Example 1-2] 5- (1-acetoxy-
5-methoxypentyl) -2-norbornene (Mono)
Synthesis of mer2) 5- (1-hydroxy-5-methoxypentyl) -2-
105.2 g of norbornene (Monomer 1) was reacted with 61.3 g of acetic anhydride in 63.3 g of pyridine in the presence of 2 g of 4-dimethylaminopyridine at room temperature for 10 hours. After stopping the reaction by adding 30 g of water, the mixture was extracted with hexane. The obtained organic layer was washed with water, dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to obtain an oily substance. This was distilled under reduced pressure to obtain 122.4 g of 5- (1-acetoxy-5-methoxypentyl) -2-norbornene. The yield was 97.0%. IR (thin film): ν = 3057, 2939, 2868, 1
732, 1458, 1373, 1338, 1244, 1
120, 1020, 723 cm- ¹ 5- (1-acetoxy-5-methoxypentyl) -2-
Of norbornene (exo body: endo body = 45: 55)
¹ H-NMR (270 MHz in CDCl ₃ ): δ
= 0.52-0.59 (0.55H, ddd, J = 1
1.7, 4.9, 2.4 Hz), 0.70-0.77
(0.45H, ddd, J = 11.7, 4.4, 2.4
Hz), 1.10-1.82 (10H, m), 1.98
(1.35H, s), 2.05 (1.65H, s),
2.15 to 2.57 (1H, m), 2.76 (2H, b
r. s), 3.29 (1.65H, s), 3.30
(1.35H, s), 4.29-4.46 (1H,
m), 5.85-5.90 (1H, m), 6.11-
6.18 (1H, m).

[Synthesis Example 1-3] Synthesis of 5- {2- (2-hydroxy-6-methoxyhexyl)}-2-norbornene (Monomer 3) In place of 5-norbornene-2-carbaldehyde, 5-
Synthesis Example 1 except that acetyl-2-norbornene was used.
In the same manner as in 1, 5- {2- (2-hydroxy-
(6-Methoxyhexyl)}-2-norbornene was synthesized. The yield was 74%. IR (thin film): ν = 3572, 3485 (br.), 3
057,2968,2939,2868,1710,1
682, 1570, 1464, 1460, 1373, 1
369, 1338, 1294, 1271, 1255, 1
238,1196,1119,931,742,719
cm ^-1 5- {2- (2-hydroxy-6-methoxyhexyl)}-2-norbornene (exo form: endo form = 4)
8:52) ¹ H-NMR (300 MHz in CD)
Cl ₃ ): δ = 1.00 (1.44H, s), 1.05
−1.16 (2.56H, m) (1.16 (1.56H, m)
H, s)), 1.18-1.63 (9H, m)
1.74-1.86 (1H, m), 2.18-2.25
(1H, m), 2.80 (1H, br.s), 2.91
(1H, br.s), 3.31-3.41 (5H, m)
(3.31 (1.56H, s), 3.32 (1.44
H, s)), 6.06-6.10 (1H, m),
6.20-6.24 (1H, m).

[Synthesis Example 1-4] 5- (2-acetoxy-
5-methoxypentyl) -2-norbornene (Mono)
Synthesis of mer4) Instead of 5-norbornene-2-carbaldehyde (5
5- (2-hydroxy-5-methoxypentyl) -2-norbornene was synthesized in the same manner as in Synthesis Example 1-1 except that (-norbornen-2-yl) acetaldehyde was used. The yield was 73%. 5- (1-hydroxy-5-methoxypentyl) -2-
5- (2-acetoxy-5-methoxypentyl) -2 was prepared in the same manner as in Synthesis Example 1-2 except that 5- (2-hydroxy-5-methoxypentyl) -2-norbornene was used instead of norbornene. -Norbornene was synthesized. The yield was 95%. IR (thin film): ν = 3057, 2958, 2868, 1
736, 1448, 1373, 1244, 1120, 1
022,719cm ^-1 5- (2- acetoxy-5-methoxy) -2-
¹ H-NM of major isomer (endo form) of norbornene
R (270 MHz in CDCl ₃ ): δ = 0.46
−0.57 (1H, m), 1.12-1.63 (8H,
m), 1.78-1.88 (1H, m), 1.93-
2.01 (4H, m) (including 2.01 (3H, s)), 2.73 (1H, br.s), 2.78 (1H,
br. s), 3.28-3.34 (5H, m) (3.3
0 (3H, s), 4.89 (1H, m), 5.
85-5.94 (1H, m), 6.07-6.11 (1
H, m).

[0145]

Embedded image

[Synthesis Example 2-1] Synthesis of Polymer 1 42.1 g of Monomer 1 and 78.1 g of 2-ethyl-2-norbornyl 5-norbornene-2-carboxylate and 49.0 g of maleic anhydride were added to 150 ml of tetrahydrofuran. And 1.8 g of 2,2′-azobis (2-methylbutyronitrile) was added. 1 at 60 ° C
After stirring for 5 hours, the mixture was concentrated under reduced pressure. The obtained residue is 6
Dissolve in 00 ml of tetrahydrofuran and add 10 L of n-
It was added dropwise to hexane. The resulting solid was collected by filtration, washed with 10 L of n-hexane, and vacuum-dried at 40 ° C. for 6 hours to obtain 86.7 g of Polymer 1 shown below.
Was obtained. Yield 51.2%
Met. The thus obtained polymer was analyzed by GPC. As a result, the weight average molecular weight (Mw) was 8100 in terms of polystyrene, and the degree of dispersion (Mw / Mn) was 1.78.
It was confirmed that it was a polymer. Also, ¹³ C-N
From MR, it was confirmed that the ratio of Monomer 1-5-norbornene-2-carboxylate 2-ethyl-2-norbornyl / maleic anhydride in the polymer was 0.2 / 0.3 / 0.5.

[Synthesis Examples 2 to 15] Polymers 2-1
Synthesis of Polymer 5 in the same manner as described above or by a known formulation.
2 to 15 were synthesized.

[0148]

Embedded image

[0149]

Embedded image

[0150]

Embedded image

[Examples] [Example I] The polymer adhesion of the polymer of the present invention was evaluated when it was mixed with a resist material as a base resin.

[Examples I-1 to I-5 and Comparative Examples 1 and 2] Polymers (Polymer 1 to 5) represented by the above formulas and polymers represented by the following formulas (Polymer) as comparisons
16, 17) was used as a base resin, and an acid generator (PAG1) represented by the following formula, a basic compound, and a solvent were mixed in the composition shown in Table 1. Then they are Teflon (registered trademark)
The solution was filtered through a filter (pore size: 0.2 μm) to obtain a resist material.

[0153]

Embedded image

[0154]

Embedded image

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

[0156]

[Table 1] The amount in parentheses is the amount (parts by weight)

In Table 1, the solvents and the basic compounds are as follows. All solvents are FC-43
0 (manufactured by Sumitomo 3M Limited) was used. PGMEA: propylene glycol methyl ether acetate TBA: tributylamine From the results in Table 1, it was confirmed that the polymer compound of the present invention had high substrate adhesion.

Example II The resist composition of the present invention was evaluated for its resolving power in KrF excimer laser exposure.

Examples II-1 to 21 Evaluation of resist resolution Polymers represented by the above formula (Polymers 1 to 15)
Is a base resin, and an acid generator represented by the following formula (PAG)
1, 2), a dissolution controlling agent represented by the following formula (DRR1
4), a basic compound, a compound represented by the following formula:
Compound having a group represented by COOH (ACC1, 2)
And the solvent were mixed in the composition shown in Table 2. Next, they were filtered with a Teflon filter (pore size: 0.2 μm) to obtain a resist material.

[0160]

Embedded image

[0161]

Embedded image

[0162]

Embedded image

The resist solution was spin-coated on a silicon wafer sprayed with hexamethyldisilazane at 90 ° C. for 90 seconds, and heat-treated at 110 ° C. for 90 seconds to form a film having a thickness of 0.5
A μm resist film was formed. This was exposed using a KrF excimer laser stepper (manufactured by Nikon Corporation, NA = 0.5), and after a heat treatment at 110 ° C. for 90 seconds,
Paddle development was performed for 60 seconds using a 2.38% aqueous solution of tetramethylammonium hydroxide to form a 1: 1 line and space pattern. A material obtained by cleaving the wafer as developed was observed by SEM (Scanning Electron Microscope), 1 line-and-space of 0.30 .mu.m: exposure to 1 resolution at (optimum exposure amount = Eop, mJ / ^cm 2)
The minimum line width (μm) of the separated line and space in was used as the resolution of the evaluation resist. Table 2 shows the composition of each resist and the evaluation results.

[0164]

[Table 2] The amount in parentheses is the amount (parts by weight)

In Table 2, the solvents and the basic compounds are as follows. All solvents are FC-43
0 (manufactured by Sumitomo 3M Limited) was used. PGMEA: Propylene glycol methyl ether acetate TEA: Triethanolamine TMMEA: Trismethoxymethoxymethoxyethylamine TMMEA: Trismethoxyethoxymethoxyethylamine From the results in Table 2, the resist material of the present invention shows that the resist material of the present invention has high sensitivity and high resolution in KrF excimer laser exposure. Sex was confirmed.

Example III The resist material of the present invention was evaluated for resolution in ArF excimer laser exposure.

[Examples III-1 and II] Evaluation of resolution of resist A resist material having the composition shown in Table 3 was prepared in the same manner as described above. The resist solution was spin-coated on a silicon wafer sprayed with hexamethyldisilazane at 90 ° C. for 90 seconds.
Heat treatment was performed at 0 ° C. for 90 seconds to form a resist film having a thickness of 0.5 μm. This was exposed to light using an ArF excimer laser stepper (manufactured by Nikon Corporation, NA = 0.55), subjected to a heat treatment at 110 ° C. for 90 seconds, and then 2.38.
% Paddle development using an aqueous solution of tetramethylammonium hydroxide for 60 seconds to form a 1: 1 line and space pattern. Observe the cross section of the developed wafer by SEM (scanning electron microscope).
The minimum line width (μ) of a separated line and space at an exposure amount (optimum exposure amount = Eop, mJ / cm ² ) at which a 0.25 μm line and space is resolved at 1: 1.
m) was taken as the resolution of the evaluation resist. Table 3 shows the composition of each resist and the evaluation results.

[0168]

[Table 3] The amount in parentheses is the amount (parts by weight)

In Table 3, the solvents and basic compounds are as follows. All solvents are FC-43
0 (manufactured by Sumitomo 3M Limited) was used. PGMEA: propylene glycol methyl ether acetate TEA: triethanolamine TMMEA: trismethoxymethoxyethylamine From the results in Table 3, it was confirmed that the resist material of the present invention had high sensitivity and high resolution in ArF excimer laser exposure. Was.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H01L 21/027 H01L 21/30 502R (72) Inventor Mutsuo Nakajima 28, Nishifukushima, Katsujo-mura, Kushiro-mura, Nakakubijo-gun, Niigata Prefecture -1 Shin-Etsu Chemical Co., Ltd. Research Center for Newly Functional Materials Technology (72) Inventor Tsunehiro Nishi 28-1 Nishi-Fukushima, Oku-ku, Nukushiro-mura, Nakakibijo-gun, Niigata Prefecture F-term (Ref.) 2H025 AA01 AA02 AA03 AA09 AB16 AC04 AC06 AC08 AD03 BE00 BG00 FA01 FA03 FA12 FA17 4H006 AA01 AA03 AB46 BJ10 BP10 GP01 GP10 KA30 4J032 CA36 CB01 CB04 CC03 4J100 AK32R AL08Q AM43R AR11P AR10QBA03 BC02

Claims (8)

[Claims] 1. An ether compound represented by the following general formula (1). Embedded image (In the formula, R ¹ is a hydrogen atom or a straight chain having 1 to 6 carbon atoms;
Shows a branched or cyclic alkyl group. R ² has 1 to 1 carbon atoms
6 represents a linear, branched or cyclic alkyl group. R ³
Represents a hydrogen atom, or an acyl group or an alkoxylcarbonyl group having 1 to 15 carbon atoms, and a part or all of the hydrogen atoms on the constituent carbons may be substituted with a halogen atom. k is 0 or 1, m is an integer of 0 to 3, and n is an integer of 3 to 6. ) 2. The following general formula (1-1) or (1-2) using an ether compound represented by the above general formula (1) as a raw material.
And a weight average molecular weight of 1,
A polymer compound having a molecular weight of 000 to 500,000. Embedded image (In the formula, k, m, n, and R ^{1 to} R ³ have the same meanings as described above.) 3. The repetition represented by the general formula (1-1)
In addition to the repeating unit, a repeating unit represented by the following general formula (2-1)
3. The composition according to claim 2, further comprising:
Child compound. Embedded image(Where k is the same as above. R⁴Is a hydrogen atom,
Or CH₂CO₂R ⁶Is shown. R⁵Is a hydrogen atom,
Cyl group or CO₂R⁶Is shown. R⁶Has 1 to 15 carbon atoms
It represents a linear, branched or cyclic alkyl group. R⁷Is an acid
Shows an unstable group. R⁸Is halogen atom, hydroxyl group, carbon number
1 to 15 linear, branched or cyclic alkoxy groups,
A siloxy group or an alkylsulfonyloxy group, or
Is a linear, branched or cyclic alkoxy having 2 to 15 carbon atoms
Represents a cyclocarbonyloxy group or an alkoxyalkoxy group
And part or all of the hydrogen atoms on the constituent carbon atoms are halogenated
And it may be substituted by a nitrogen atom. Z is a single bond or carbon number
1-5 linear, branched or cyclic (p + 2) -valent carbonized
Represents a hydrogen group, and when it is a hydrocarbon group, one or more
Methylene is replaced by oxygen to form a chain or cyclic ether
Or two hydrogens on the same carbon are replaced by oxygen
To form a ketone. p is 0, 1 or 2
You. ) 4. The repetition represented by the general formula (1-1)
In addition to the formula unit, it is represented by the following general formulas (2-1) and (3).
3. A repeating unit comprising:
The polymer compound as described in the above. Embedded image(Where Z, k, p, R⁴~ R⁸Is the same as above.
Y is an oxygen atom, or NR ⁹And R⁹Has 1 to 6 carbon atoms
Represents a linear, branched or cyclic alkyl group. ) 5. In addition to the repeating unit represented by the general formula (1-1), a repeating unit represented by the following general formula (4) or a repeating unit represented by the following general formula (4) and a compound represented by the following general formula (4) The polymer compound according to claim 2, further comprising a repeating unit represented by 2-1) and a repeating unit represented by the following general formula (3). Embedded image (In the formula, Y, Z, k, p, and R ^{4 to} R ⁹ are the same as above.) 6. The polymer compound according to claim 2, comprising a repeating unit represented by the following general formula (2-2) in addition to the repeating unit represented by the general formula (1-2). . Embedded image (In the formula, Z, k, p, and R ^{4 to} R ⁸ are the same as described above.) 7. A resist material comprising the polymer compound according to claim 2. Description: 8. A step of applying the resist material according to claim 7 on a substrate, a step of exposing with a high energy beam or an electron beam through a photomask after heat treatment, and a step of subjecting to heat treatment if necessary. And developing using a developing solution.