JP2003084440A - Resist material and pattern forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resist material such as a chemical amplification type resist material having very high contrast between velocity of dissolution in alkali before exposure and that after exposure, high sensitivity, high resolution and particularly excellent etching resistance and suitable for use as a fine pattern forming material particularly for production of VLSI (very large scale integrated circuit). SOLUTION: The resist material comprises a high molecular compound having a weight average molecular weight of 1,000-500,000 and containing repeating units of formula (1) and repeating units having an acid-labile group. In the formula, R<1> is H, hydroxy, a 1-4C linear or branched alkyl, a 1-20C substitutable alkoxy or halogen; (m) is 0 or a positive integer of 1-4; X is O, S or -NR-, wherein R is H, a 1-4C linear or branched alkyl or hydroxy; and (p) is a positive number.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention has a significantly high alkali dissolution rate contrast before and after exposure, has high sensitivity and high resolution, and exhibits extremely excellent etching resistance. The present invention relates to a chemically amplified positive resist material suitable as a fine pattern forming material for a mask and a pattern forming method.

[0002]

2. Description of the Related Art In recent years,
With the higher integration and higher speed of LSIs, deep-UV lithography has been put into practical use in response to the demand for finer pattern rules. Far-ultraviolet lithography is 0.5μ
Processing of m or less is also possible, and when a resist material having low light absorption is used, it becomes possible to form a pattern having a side wall that is nearly vertical to the substrate.

For example, a chemically amplified positive resist material using an acid catalyst (Japanese Patent Publication No. 27660/1990, JP-A-63).
-27829 gazette) is a resist material for deep ultraviolet lithography, which uses a high-intensity KrF excimer laser as a deep ultraviolet light source, has high sensitivity, resolution, and high dry etching resistance and has excellent characteristics. is there.

As such a chemically amplified positive resist material, a two-component system comprising a base polymer and an acid generator,
A three-component system comprising a base polymer, an acid generator and a dissolution inhibitor having an acid labile group is known.

For example, Japanese Patent Application Laid-Open No. 62-115440 proposes a resist material comprising poly-p-tert-butoxystyrene and an acid generator, and Japanese Patent Application Laid-Open No. 3-223858 discloses a resist material similar to this proposal. T in the molecule
A two-component resist material comprising an ert-butoxy group-containing resin and an acid generator, and further, JP-A-4-21258 discloses a methyl group, an isopropyl group, a tert-butyl group, a tetrahydropyranyl group, a trimethylsilyl group-containing poly A two-component resist material composed of hydroxystyrene and an acid generator has been proposed.

Further, JP-A-6-100488 discloses that poly [3,4-bis (2-tetrahydropyranyloxy) styrene], poly [3,4-bis (tert-butoxycarbonyloxy) styrene], poly A resist material comprising a polydihydroxystyrene derivative such as [3,5-bis (2-tetrahydropyranyloxy) styrene] and an acid generator has been proposed.

However, the base resin of these resist materials has an acid labile group in the side chain, and the acid labile group is decomposed by a strong acid such as tert-butyl group and tert-butoxycarbonyl group. Then, the pattern shape of the resist material is likely to be a T-top shape, and on the other hand, an alkoxyalkyl group such as an ethoxyethyl group is decomposed by a weak acid. Therefore, with the passage of time from exposure to heat treatment, There is a problem that the pattern shape is extremely thin, or because it has a bulky group in the side chain, heat resistance is lowered, sensitivity and resolution are not satisfactory, both have problems, Studies have been made to compensate for the drawbacks by using these plural substituents.

In addition, a copolymer of hydroxystyrene and a (meth) acrylic acid tertiary ester is used in order to realize higher transparency and adhesion to the substrate, improve footing up to the substrate, and improve etching resistance. The above resist materials have also been reported (JP-A-3-275149, JP-A-6-
No. 289608), however, this type of resist material has problems such as heat resistance and a poor pattern shape after exposure, and it is not satisfactory in etching resistance.

Further, at present, with the progress of higher resolution,
Thinning of the resist pattern is also progressing at the same time, and accordingly, a resist material having higher etching resistance is desired.

The present invention has been made in view of the above circumstances.
A resist material having higher sensitivity and resolution than conventional resist materials, exposure allowance, process adaptability, a good pattern shape after exposure, and excellent etching resistance, particularly a chemically amplified positive resist material. And it aims at providing a pattern formation method.

[0011]

Means for Solving the Problems and Modes for Carrying Out the Invention As a result of extensive studies conducted by the present inventor to achieve the above object, the following general formula (1), (2), (3) or (4) And has a weight average molecular weight of 1,00.
A polymer compound of 0 to 500,000 is effective as a base resin for a resist material, particularly a chemically amplified positive resist material, and a chemically amplified positive resist material containing this polymer compound, an acid generator and an organic solvent is used as a resist. The film has high dissolution contrast, high resolution, good exposure latitude, excellent process adaptability, good pattern shape after exposure, and better etching resistance. As a result, they have found that it is very effective as a resist material for VLSI, and completed the present invention.

Therefore, the present invention provides the following resist material and pattern forming method. [Claim 1] A polymer compound containing a repeating unit represented by the following general formula (1) and a repeating unit having an acid labile group and having a weight average molecular weight of 1,000 to 500,000. Resist material.

[Chemical 9] (In the formula, R ¹ is a hydrogen atom, a hydroxy group, or a carbon number of 1 to 4
A linear or branched alkyl group having 1 to 20 carbon atoms
Represents a substitutable alkoxy group or a halogen atom. Further, m is 0 or a positive integer of 1 to 4. X represents an oxygen atom, a sulfur atom, or a -NR- group, R represents a hydrogen atom,
It is a linear or branched alkyl group having 1 to 4 carbon atoms, or a hydroxy group. p is a positive number. (2) A polymer compound containing a repeating unit represented by the following general formula (2) and a repeating unit having an acid labile group and having a weight average molecular weight of 1,000 to 500,000. Resist material.

[Chemical 10] (In the formula, R ¹ and R ² are the same or different hydrogen atoms, a hydroxy group, a linear or branched alkyl group having 1 to 4 carbon atoms, a substitutable alkoxy group having 1 to 20 carbon atoms, or a halogen atom. In addition, m and n are 0 or a positive integer of 1 to 4. X represents an oxygen atom, a sulfur atom, or a —NR— group, R represents a hydrogen atom, a straight chain having 1 to 4 carbon atoms. A branched or branched alkyl group or a hydroxy group, and p and q are positive numbers.) Claim 3: A polymer compound having a repeating unit represented by the following general formula (3). Resist material.

[Chemical 11] (In the formula, R¹, X, m, p are R as described above.³Is a hydrogen atom
Or represents a methyl group, R ^FourIs a hydrogen atom, methyl group,
Represents a coxycarbonyl group, a cyano group, or a halogen atom.
And R^FiveRepresents an acid labile group. R is a positive number
It ) Claim 4: A repeating unit represented by the following general formula (4)
Resin containing a polymer compound having
Material.

[Chemical 12] (In the formula, R ¹ , R ³ , R ⁴ , R ⁵ , and X are as described above, R ⁶ is a hydrogen atom or a methyl group, m, p, and r are as described above, and o is 0 or 1 to 1. 4 is a positive integer and s is a positive number.) Claim 5: A resist material containing a polymer compound having a repeating unit represented by the following general formula (5).

[Chemical 13] (In the formula, R ¹ , R ² , and X are as described above, R ³ represents a hydrogen atom or a methyl group, R ⁴ represents a hydrogen atom, a methyl group, an alkoxycarbonyl group, a cyano group, or a halogen atom; ⁵ represents an acid labile group, and m and n are 0 or 1.
Is a positive integer of ˜4. Further, p and q are positive numbers, and r is a positive number. ] Claim 6: The resist material containing the high molecular compound which has a repeating unit shown by the following general formula (6).

[Chemical 14] (In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and X are as described above.
R ⁶ represents a hydrogen atom or a methyl group, m, n, q and p are as described above, o is 0 or a positive integer of 1 to 4, and s
Is a positive number. ) Claim 7: In the resist material according to any one of claims 1 to 6, the repeating unit p is represented by the following general formula (1a).
A resist material characterized by being represented by:

[Chemical 15] (In the formula, R ⁵ and X are as described above, p is a positive number, and m is 0 or a positive integer of 1 to 4.) Claim 8: The resist material according to Claim 2, 5 or 6. In the resist material, the repeating unit q is represented by the following general formula (2a).

[Chemical 16] (In the formula, R ² and R ⁵ are as described above, q is a positive number, and m is 0 or a positive integer of 1 to 4.) Claim 9: (A) organic solvent, (B) base The polymer compound according to any one of claims 1 to 8 as a resin,
(C) A chemically amplified positive resist composition containing an acid generator. Claim 10: (A) an organic solvent, (B) a high molecular compound according to any one of claims 1 to 8 as a base resin,
A chemically amplified positive resist composition containing (C) an acid generator and (D) a dissolution inhibitor. [11] The chemically amplified positive resist composition according to [9] or [10], which further comprises a basic compound as an additive (E). Claim 12: A step of applying the resist material according to any one of claims 1 to 11 on a substrate, a step of exposing with a high energy beam or an electron beam through a photomask after heat treatment, if necessary. And a developing process using a developing solution after the heat treatment.

The present invention will be described in more detail below.
The resist material of the present invention contains a polymer compound having a repeating unit represented by the following general formulas (1) to (6) as a base resin.

[0014]

[Chemical 17]

Here, R ¹ and R ² are each a hydrogen atom,
A hydroxy group, preferably a linear or branched alkyl group having 1 to 4 carbon atoms, preferably a substitutable alkoxy group having 1 to 20 carbon atoms, particularly 1 to 12 carbon atoms, or a halogen atom is shown. The alkoxy group may have some or all of its hydrogen atoms substituted with an alkyl group.

Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group and the like, and examples of the substitutable alkoxy group include methoxy group. Group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, t-butoxy group and the like, and the halogen atom includes fluorine atom, chlorine atom, bromine atom and the like.

X is an oxygen atom, a sulfur atom or a --NR-- group, and R is a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a hydroxy group.

R ³ and R ⁶ represent a hydrogen atom or a methyl group, and R ⁴ is a hydrogen atom, a methyl group, preferably an alkoxycarbonyl group having 2 to 10 carbon atoms, particularly 2 to 8 carbon atoms, a cyano group, or the above. R ⁵ represents an acid labile group, which will be described later.

M, n, and o are 0, 1, 2, 3, and 4, respectively, and p, q, r, and s are positive numbers, which will be described later.

In the general formulas (1) to (6), p unit, q
In the case of a repeating unit having an acid labile group, the p unit and q unit can be represented by the following general formula.

[0021]

[Chemical 18] Here, R ⁵ is an acid labile group.

As the monomer giving the repeating unit p, indole derivatives shown in the following (p-1) to (p-9), benzofuran derivatives shown in the following (p-10) to (p-12), The following (p-13) to (p-1
The benzothiophene derivative shown in 5) can be mentioned.

[Chemical 19]

Examples of the monomer that gives the repeating unit q include the substituted or unsubstituted indene derivatives represented by the following (q-1) to (q-12).

[0024]

[Chemical 20]

Various kinds of acid labile groups for R ⁵ are selected. Particularly, groups represented by the following formulas (A-1) and (A-2) and carbons represented by the following formula (A-3) are selected. A tertiary alkyl group having 4 to 20 carbon atoms, a trialkylsilyl group in which each alkyl group has 1 to 6 carbon atoms, an oxoalkyl group having 4 to 20 carbon atoms, and the like are preferable.

[0026]

[Chemical 21]

In the formula (A-1), R ³⁰ has 4 to 4 carbon atoms.
20, preferably a 4 to 15 tertiary alkyl group, each alkyl group is a C1 to C6 trialkylsilyl group,
An oxoalkyl group having 4 to 20 carbon atoms or the above general formula (A
-3), and specifically as a tertiary alkyl group, a tert-butyl group, a tert-amyl group,
1,1-diethylpropyl group, 1-ethylcyclopentyl group, 1-butylcyclopentyl group, 1-ethylcyclohexyl group, 1-butylcyclohexyl group, 1-ethyl-2-cyclopentenyl group, 1-ethyl-2-cyclohexenyl group Group, a 2-methyl-2-adamantyl group, and the like. Specific examples of the trialkylsilyl group include a trimethylsilyl group, a triethylsilyl group, and dimethyl-ter.
Examples thereof include a t-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- group.
Examples include 2-oxooxolan-5-yl group. a
Is an integer of 0 to 6.

In the formula (A-2), R ³¹ and R ³² represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, and specifically, Methyl group, ethyl group, propyl group, isopropyl group, n-
Examples thereof include a butyl group, sec-butyl group, tert-butyl group, cyclopentyl group, cyclohexyl group, 2-ethylhexyl group, n-octyl group and the like. R ³³ has 1 carbon atom
To 18, preferably 1 to 10, a monovalent hydrocarbon group which may have a hetero atom such as an oxygen atom, and is a linear, branched or cyclic alkyl group, and some of these hydrogen atoms are Examples thereof include those substituted with a hydroxyl group, an alkoxy group, an oxo group, an amino group, an alkylamino group and the like, and specific examples include the following substituted alkyl groups.

[0029]

[Chemical formula 22]

R ³¹ and R ³² , R ³¹ and R ³³ , and R ³² and R ³³ may be bonded to each other to form a ring. In the case of forming a ring, R ³¹ , R ³² and R ³³ are Each represents a linear or branched alkylene group having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms.

As the acid labile group of the above formula (A-1),
Specifically, a tert-butoxycarbonyl group, tert
-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.

Further, the following formulas (A-1) -1 to (A-1)
The substituent shown by -9 can also be mentioned.

[0033]

[Chemical formula 23]

Here, R ³⁷ is the same or different from each other and is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 17 carbon atoms, and R ³⁸ is a hydrogen atom or a carbon atom. It is a linear, branched or cyclic alkyl group of the number 1 to 10.

R ³⁹ is the same or different from each other, and is a linear, branched or cyclic alkyl group having 2 to 10 carbon atoms,
Alternatively, it is an aryl group having 6 to 20 carbon atoms.

Among the acid labile groups represented by the above formula (A-2), those having a linear or branched structure are represented by the following formula (A-
2) -1 to (A-2) -23 can be exemplified.

[0037]

[Chemical formula 24]

[0038]

[Chemical 25]

Among the acid labile groups represented by the above formula (A-2), a cyclic one is tetrahydrofuran-2-
Yl group, 2-methyltetrahydrofuran-2-yl group,
Examples thereof include a tetrahydropyran-2-yl group and a 2-methyltetrahydropyran-2-yl group.

The general formula (A-2a) or (A-
The base resin may be intermolecularly or intramolecularly crosslinked by the acid labile group represented by 2b).

[0041]

[Chemical formula 26]

In the formula, R ⁴⁰ and R ⁴¹ are hydrogen atoms or have 1 carbon atom.
8 represents a linear, branched or cyclic alkyl group. Alternatively, R ⁴⁰ and R ⁴¹ may combine with each other to form a ring, and when forming a ring, R ⁴⁰ and R ^{41 each} represent a linear or branched alkylene group having 1 to 8 carbon atoms. R ⁴² is a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, b and d are 0 or 1 to 10, preferably an integer of 0 or 1 to 5 and c is 1 to
It is an integer of 7. A is a (c + 1) -valent carbon number 1 to 50
Represents an aliphatic or alicyclic saturated hydrocarbon group, an aromatic hydrocarbon group or a heterocyclic group, and these groups may have a heteroatom interposed, or a part of hydrogen atoms bonded to the carbon atom It may be substituted with a hydroxyl group, a carboxyl group, a carbonyl group or a fluorine atom. B is -CO-
O-, -NHCO-O- or -NHCONH- is shown.

In this case, A is preferably a divalent to tetravalent C1-C20 linear, branched or cyclic alkylene group, an alkyltriyl group, an alkyltetrayl group and a C6-C30. It is an arylene group, and these groups may have a heteroatom interposed, and a part of hydrogen atoms bonded to the carbon atom may be substituted with a hydroxyl group, a carboxyl group, an acyl group or a halogen atom. Further, c is preferably an integer of 1 to 3.

The cross-linking acetal groups represented by formulas (A-2a) and (A-2b) are specifically represented by the following formula (A-
2) -24 to (A-2) -31.

[0045]

[Chemical 27]

Next, in the formula (A-3), R ³⁴ , R ³⁵ ,
R ³⁶ is a straight-chain having 1 to 18 carbon atoms or a monovalent hydrocarbon group, branched or cyclic alkyl group, oxygen, sulfur, nitrogen, which may contain a hetero atom such as fluorine, R ³⁴ and R
³⁵ , R ³⁴ and R ³⁶ , and R ³⁵ and R ³⁶ may be bonded to each other to form a ring having 3 to 19 carbon atoms together with the carbon atom to which they are bonded.

The tertiary alkyl group represented by the formula (A-3) includes a tert-butyl group, a triethylcarbyl group,
1-ethylnorbornyl group, 1-methylcyclohexyl group, 1-ethylcyclopentyl group, 2- (2-methyl)
Adamantyl group, 2- (2-ethyl) adamantyl group,
Examples thereof include a tert-amyl group.

As the tertiary alkyl group, the following formulas (A-3) -1 to (A-3) -18 can be specifically mentioned.

[0049]

[Chemical 28]

In formulas (A-3) -1 to (A-3) -18,
R ⁴³ represents the same or different, straight-chain, branched or cyclic alkyl group having 1 to 8 carbon atoms or aryl group such as phenyl group having 6 to 15 carbon atoms. R ^44, R ⁴⁶ is a hydrogen atom, or a straight, an alkyl group branched or cyclic. R ⁴⁵ represents an aryl group having 6 to 20 carbon atoms such as a phenyl group.

Further, the following formulas (A-3) -19, (A-3)
As shown in -20, the polymer may be crosslinked intramolecularly or intermolecularly by including R ⁴⁷ which is a divalent or higher valent alkylene group or an arylene group. Formula (A-3) -19,
In (A-3) -20, R ⁴³ is the same as described above, R ⁴⁷ is a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms, or an arylene group such as a phenylene group, and an oxygen atom or It may contain a hetero atom such as a sulfur atom or a nitrogen atom. b1 is an integer of 1 to 3.

[0052]

[Chemical 29]

Further, R ³⁴ , R ³⁵ and R ^{36 in the} formula (A-3) are
May have a hetero atom such as oxygen, nitrogen or sulfur, and specific examples thereof include those represented by the following formulas (A) -1 to (A) -7.

R ³⁰ , R ³³ and R ³⁶ in the formulas (A-1), (A-2) and (A-3) are phenyl group, p-methylphenyl group, p-ethylphenyl group and p- Unsubstituted or substituted aryl groups such as alkoxy-substituted phenyl groups such as methoxyphenyl group, aralkyl groups such as benzyl group, phenethyl group, etc., and those groups having an oxygen atom or a hydrogen atom bonded to a carbon atom is a hydroxyl group. An alkyl group represented by the following formulas (A) -1 to (A) -7, which is substituted or two hydrogen atoms are substituted with oxygen atoms to form a carbonyl group, or a formula (A) -8, The oxoalkyl group shown by (A) -9 can be mentioned.

[0055]

[Chemical 30]

Examples of the trialkylsilyl group in which each alkyl group used as the acid labile group for R ⁵ has 1 to 6 carbon atoms include a trimethylsilyl group, a triethylsilyl group and a tert-butyldimethylsilyl group.

Examples of the oxoalkyl group having 4 to 20 carbon atoms include a 3-oxocyclohexyl group and a group represented by the following formula.

[0058]

[Chemical 31]

As the repeating unit of the polymer compound used as the base resin of the resist material of the present invention, the p unit is an essential unit, but 0.02 ≦ p / (p + q + r +
s) ≦ 0.7, especially 0.05 ≦ p / (p + q + r + s)
It is preferable that ≦ 0.5. Further, in the case of the polymer compounds represented by the formula (2) and the formulas (5) and (6), q unit is also essential, but in this case, 0.02 ≦ q / (p + q
+ R + s) ≦ 0.7, especially 0.05 ≦ q / (p + q + r
It is preferable that + s) ≦ 0.5.

Further, as shown in the general formulas (3) to (6), an r unit for improving the dissolution contrast can be contained, and in this case, 0.05 ≦ r / (p + q
It is preferable that + r + s) ≦ 0.6. Further, an s unit may be contained in order to improve the adhesion and the dissolution contrast. In this case, 0.05 ≦ s /
It is preferable that (p + q + r + s) ≦ 0.6. When at least one or two or more of the p unit, q unit and s unit has a hydroxy group and it is substituted with an acid labile group, for example, general formulas (1) to (6)
In the case where R ¹ is a group substituted with an acid labile group, that is, an OR ⁵ group, the r unit is not always necessary. Further, when either one or both of the p unit and the q unit has a hydroxy group and it is substituted with an acid labile group, both the r unit and the s unit are not necessarily required.

In the equations (1) to (6), p, p
+ Q, p + r, p + r + s, p + q + r, p + q + r +
s is 0.1 ≦ p ≦ 1.0, 0.1 ≦ p + q ≦ 1.0,
0.3 ≦ p + r ≦ 1.0, 0.4 ≦ p + r + s ≦ 1.
0, 0.4 ≦ p + q + r ≦ 1.0, 0.4 ≦ p + q + r
It is preferable that + s ≦ 1.0.

Considering the characteristics of the resist material, each of the polymer compounds of the present invention has a weight average molecular weight of 1.00.
0 to 500,000, preferably 2,000 to 30,0
Must be 00. If the weight average molecular weight is too small, the resist material will be inferior in heat resistance, and if it is too large, the alkali solubility will be lowered, and the footing phenomenon will easily occur after pattern formation.

Further, in the polymer compound of the present invention,
When the molecular weight distribution (Mw / Mn) of the multi-component copolymer of the above general formulas (1) to (6) is wide, a low molecular weight or high molecular weight polymer is present, and therefore foreign matter is observed on the pattern after exposure. Or, the shape of the pattern deteriorates. Therefore,
Since the influence of such molecular weight and molecular weight distribution tends to increase as the pattern rule becomes finer, the molecular weight distribution of the multi-component copolymer to be used should be determined in order to obtain a resist material suitable for use in fine pattern dimensions. 1.0 ~
A narrow dispersion of 2.0, particularly 1.0 to 1.5 is preferable.

In the present invention, the p unit, the q unit, the r unit and the s unit have different composition ratios, molecular weight distributions and molecular weights.
It is also possible to blend two or more polymers. It is also possible to carry out polymer blending with a substituted or unsubstituted novolak, polyhydroxystyrene, polyhydroxystyrene- (meth) acrylic acid derivative or the like.
In the present invention, in addition to the constituent components represented by the p unit, q unit, r unit, and s unit, other monomer components for further improving adhesion, dry etching resistance, and transparency may be added and copolymerized. Yes, p, p + q, p + r, p +
When q + r, p + r + s, and p + q + r + s are less than 1.0, the other monomer units are combined and their sum is 1.
It can be zero. Examples of this monomer component include (meth) acrylic derivatives, norbornene derivatives,
Examples thereof include maleic anhydride, maleimide derivative, acenaphthene derivative, vinylnaphthalene derivative, vinylanthracene derivative, vinyl ether derivative, allyl ether derivative, vinyl acetate, (meth) acrylonitrile, vinylpyrrolidone, and tetrafluoroethylene.

Radical polymerization is the most general method for synthesizing the polymer compound used in the resist material of the present invention.
Although indene does not polymerize by radical polymerization, it can be copolymerized with a (meth) acryl derivative, indole, benzofuran or benzothiophene, and also with styrene and hydroxystyrene. Cationic polymerization is generally used for copolymerization of indene with indole, benzofuran or benzothiophene, or homopolymerization of indole, benzofuran or benzothiophene.

One method for synthesizing these polymer compounds is to use a styrene monomer, a (meth) acrylic acid tertiary ester monomer, an indene monomer, an indole monomer, a benzofuran monomer, and a benzothiophene monomer in an organic solvent. , A radical initiator was added, and the mixture was heated and polymerized, the obtained polymer compound was subjected to alkaline hydrolysis in an organic solvent to deprotect the acetoxy group, hydroxystyrene and (meth) acrylic acid tertiary ester, and indene, It is possible to obtain a polymer compound of a four-component copolymer of indole, benzofuran or benzothiophene. As the organic solvent used during the polymerization, toluene,
Examples thereof include benzene, tetrahydrofuran, diethyl ether and dioxane. As the radical polymerization initiator, 2,2'-azobisisobutyronitrile, 2,2 '
-Azobis (2,4-dimethylvaleronitrile), dimethyl-2,2-azobis (2-methylpropionate), benzoyl peroxide, lauroyl peroxide and the like can be illustrated.

Cationic polymerization initiators include sulfuric acid and phosphorus.
Acid, hydrochloric acid, nitric acid, hypochlorous acid, trichloroacetic acid, trif
Luoroacetic acid, methanesulfonic acid, trifluoromethane
Rufonic acid, camphorsulfonic acid, tosylic acid, etc.
Acid, BF₃, AlCl₃, TiCl _Four, SnCl_FourSuch as
In addition to Riedel Crafts catalyst, I₂, (C₆H_Five)₃CCl
Substances that easily generate cations are used.

The reaction can be polymerized by heating preferably at 50 ° C to 80 ° C. The reaction time is 2 to 100 hours,
It is preferably 5 to 20 hours. Ammonia water, triethylamine and the like can be used as the base for the alkali hydrolysis. The reaction temperature is −20 to 100 ° C., preferably 0 to 60 ° C., and the reaction time is 0.2 to
It is 100 hours, preferably 0.5 to 20 hours.

When the styrene monomer, the indene monomer, the indole monomer, the benzofuran monomer, and the benzothiophene monomer have a phenolic hydroxyl group, it is possible to polymerize as it is, but it is better to polymerize after substitution with an acetoxy group or the like. The degree can be reduced. At this time, the acetoxy group can be converted to a hydroxy group by polymerizing and then hydrolyzing with alcal water. Further, the hydrogen atom of the phenolic hydroxyl group of the styrene monomer, the indene monomer, the indole monomer, the benzofuran monomer, and the benzothiophene monomer may be replaced with an acid labile group before polymerization.

Further, after the polymer compound thus obtained is isolated, it is represented by the general formulas (A-1), (A-2) and (A-3) with respect to the phenolic hydroxyl group moiety. It is also possible to introduce acid labile groups. For example, it is possible to react the phenolic hydroxyl group of a polymer compound with an alkenyl ether compound in the presence of an acid catalyst to obtain a polymer compound in which the phenolic hydroxyl group is partially protected by an alkoxyalkyl group.

At this time, the reaction solvent is preferably an aprotic polar solvent such as dimethylformamide, dimethylacetamide, tetrahydrofuran or ethyl acetate,
You may use it individually or in mixture of 2 or more types. Examples of the catalyst acid include hydrochloric acid, sulfuric acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, p
-Toluenesulfonic acid pyridinium salt and the like are preferable, and the amount thereof is 0.1 to 1 with respect to 1 mol of all the hydroxyl groups of hydrogen atoms of the phenolic hydroxyl group of the polymer compound which reacts.
It is preferably 0 mol%. The reaction temperature is -2
It is 0 to 100 ° C, preferably 0 to 60 ° C, and the reaction time is 0.2 to 100 hours, preferably 0.5 to 20.
It's time.

It is also possible to obtain a polymer compound in which a phenolic hydroxyl group is partially protected by an alkoxyalkyl group by reacting a halogenated alkyl ether compound with a polymer compound in the presence of a base. Is.

At this time, the reaction solvent is preferably an aprotic polar solvent such as acetonitrile, acetone, dimethylformamide, dimethylacetamide, tetrahydrofuran or dimethylsulfoxide, and may be used alone or in combination of two or more kinds. As the base, triethylamine, pyridine, diisopropylamine, potassium carbonate and the like are preferable, and the amount of the base used is such that the hydrogen atom of the phenolic hydroxyl group of the polymer compound to be reacted is 1
It is preferably 10 mol% or more based on mol. The reaction temperature is -50 to 100 ° C, preferably 0 to 60
The reaction time is 0.5 to 100 hours, preferably 1 to 20 hours.

Further, the introduction of the acid labile group of a = 0 in the above formula (A-1) is carried out by using a dialkyl dicarbonate compound or an alkoxycarbonylalkyl halide and a polymer compound.
It is possible to carry out the reaction in the presence of a base in a solvent. The reaction solvent is preferably an aprotic polar solvent such as acetonitrile, acetone, dimethylformamide, dimethylacetamide, tetrahydrofuran or dimethylsulfoxide, and may be used alone or in combination of two or more.

As the base, triethylamine, pyridine, imidazole, diisopropylamine, potassium carbonate and the like are preferable, and the amount thereof used is 10 moles of hydrogen atoms of the phenolic hydroxyl group of the original polymer compound per 1 mole of all hydroxyl groups. % Or more is preferable.

The reaction temperature is 0 to 100 ° C, preferably 0 to 60 ° C. The reaction time is 0.2 to 100
The time is preferably 1 to 10 hours.

Examples of the dialkyl dicarbonate compound include di-tert-butyl dicarbonate and di-tert-amyl dicarbonate, and examples of the alkoxycarbonylalkyl halide include tert-butoxycarbonylmethyl chloride.
tert-amyloxycarbonylmethyl chloride, t
ert-butoxycarbonylmethyl bromide, ter
Examples thereof include t-butoxycarbonylethyl chloride. However, the present invention is not limited to these synthesis methods.

The resist material of the present invention is particularly favorably used as a positive type and contains the above-mentioned polymer compound. In this case, the resist material of the present invention comprises (A) an organic solvent and (B) a base resin. As the above polymer compound,
It is preferably used as a chemically amplified positive resist material containing (C) an acid generator, and optionally (D) a dissolution inhibitor, preferably (E) a basic compound.

In the chemically amplified positive resist composition of the present invention, the organic solvent of the component (A) is butyl acetate, amyl acetate, cyclohexyl acetate, 3-methoxybutyl acetate, methyl ethyl ketone, methyl amyl ketone, cyclohexanone, Cyclopentanone, 3-ethoxyethylpropionate, 3-ethoxymethylpropionate, 3-methoxymethylpropionate, methyl acetoacetate, ethyl acetoacetate, diacetone alcohol,
Methyl pyruvate, ethyl pyruvate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether,
Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 3-methyl-3-methoxybutanol, N-methylpyrrolidone, dimethyl sulfoxide, γ-butyrolactone, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, methyl lactate, Examples thereof include ethyl lactate, propyl lactate, and tetramethylene sulfone, but are not limited to these. Particularly preferred are propylene glycol alkyl ether acetate and alkyl lactate. These solvents may be used alone or in combination of two or more. Examples of preferred mixed solvents are propylene glycol alkyl ether acetate and alkyl lactate. The alkyl group of the propylene glycol alkyl ether acetate in the present invention includes those having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group and the like. Among them, a methyl group and an ethyl group are preferable. The propylene glycol alkyl ether acetate has 1,2-substitution products and 1,3-substitution products, and there are three isomers depending on the combination of substitution positions, but either one or a mixture may be used.

The alkyl group of the alkyl lactate ester may be one having 1 to 4 carbon atoms, such as a methyl group, an ethyl group or a propyl group. Of these, a methyl group or an ethyl group is preferred.

When propylene glycol alkyl ether acetate is added as a solvent, it is 1 with respect to all the solvents.
It is preferably 0% by weight or more. When a mixed solvent of propylene glycol alkyl ether acetate and alkyl lactate is used as a solvent, the total amount thereof is preferably 50% by weight or more based on all the solvents. In this case, more preferably, 20 to 100% by weight of propylene glycol alkyl ether acetate,
It is preferable that the proportion of the alkyl lactate is 0 to 80% by weight. When the amount of propylene glycol alkyl ether acetate is small, there are problems such as deterioration of coating properties, and when the amount is too large, there are problems of insufficient solubility, generation of particles and foreign substances. When the amount of alkyl lactate is small, there is a problem that the solubility is insufficient, especially when an onium salt is added as an acid generator, and particles and foreign substances increase. When it is too large, the viscosity becomes high and the coatability deteriorates. However, there are problems such as deterioration of storage stability.

The addition amount of these solvents is 300 to 100 parts by weight of the base resin of the chemically amplified positive resist material.
Although it is 2,000 parts by weight, preferably 400 to 1,000 parts by weight, it is not limited to this as long as it is a concentration that can be achieved by the existing film forming method.

The photo-acid generator as the component (C) may be any compound as long as it is a compound capable of generating an acid upon irradiation with high energy rays. Suitable photoacid generators include sulfonium salts, iodonium salts, sulfonyldiazomethane, N-
There are sulfonyloxyimide type acid generators and the like. As described in detail below, these may be used alone or in combination of two or more.

The sulfonium salt is a salt of a sulfonium cation and a sulfonate, and triphenylsulfonium, (4-tert-butoxyphenyl) diphenylsulfonium and bis (4-ter) are used as the sulfonium cation.
t-butoxyphenyl) phenylsulfonium, tris (4-tert-butoxyphenyl) sulfonium,
(3-tert-butoxyphenyl) diphenylsulfonium, bis (3-tert-butoxyphenyl) phenylsulfonium, tris (3-tert-butoxyphenyl) sulfonium, (3,4-ditert-butoxyphenyl) diphenylsulfonium, bis ( 3,4-
Ditert-butoxyphenyl) phenylsulfonium, tris (3,4-ditert-butoxyphenyl)
Sulfonium, diphenyl (4-thiophenoxyphenyl) sulfonium, (4-tert-butoxycarbonylmethyloxyphenyl) diphenylsulfonium, tris (4-tert-butoxycarbonylmethyloxyphenyl) sulfonium, (4-tert-butoxyphenyl) bis ( 4-dimethylaminophenyl) sulfonium, tris (4-dimethylaminophenyl) sulfonium, 2-naphthyldiphenylsulfonium, dimethyl 2-naphthylsulfonium, 4-hydroxyphenyldimethylsulfonium, 4-methoxyphenyldimethylsulfonium, trimethylsulfonium, 2-oxo Examples thereof include cyclohexylcyclohexylmethylsulfonium, trinaphthylsulfonium, tribenzylsulfonium, and the like. Examples of trifluoromethane sulfonate, nonafluorobutane sulfonate, heptadecafluorooctane sulfonate, 2,2,2-trifluoroethane sulfonate, pentafluorobenzene sulfonate, 4-trifluoromethylbenzene sulfonate, 4-fluorobenzene sulfonate, toluene Examples thereof include sulfonates, benzene sulfonates, 4- (4-toluenesulfonyloxy) benzene sulfonates, naphthalene sulfonates, camphor sulfonates, octane sulfonates, dodecyl benzene sulfonates, butane sulfonates, methane sulfonates and the like, and sulfonium salts of combinations thereof.

The iodonium salt is a salt of an iodonium cation and a sulfonate, and includes diphenyliodonium, bis (4-tert-butylphenyl) iodonium and 4
-Tert-butoxyphenylphenyliodonium,
Aryl iodonium cation such as 4-methoxyphenylphenyl iodonium and trifluoromethane sulfonate, nonafluorobutane sulfonate, heptadecafluorooctane sulfonate as sulfonate, 2,
2,2-trifluoroethane sulfonate, pentafluorobenzene sulfonate, 4-trifluoromethylbenzene sulfonate, 4-fluorobenzene sulfonate, toluene sulfonate, benzene sulfonate, 4
-(4-Toluenesulfonyloxy) benzene sulfonate, naphthalene sulfonate, camphor sulfonate, octane sulfonate, dodecyl benzene sulfonate, butane sulfonate, methane sulfonate, etc. are mentioned, and the iodonium salt of these combinations is mentioned.

Examples of the sulfonyldiazomethane include bis (ethylsulfonyl) diazomethane, bis (1-methylpropylsulfonyl) diazomethane, bis (2-methylpropylsulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, bis (cyclohexyl). Sulfonyl) diazomethane, bis (perfluoroisopropylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, bis (4-methylphenylsulfonyl) diazomethane, bis (2,4-dimethylphenylsulfonyl) diazomethane, bis (2-naphthylsulfonyl) diazomethane , 4-methylphenylsulfonylbenzoyldiazomethane, tert-butylcarbonyl-4-methylphenylsulfonyldiazomethane, 2-naphthylsulfur Sulfonyl benzoyl diazomethane,
4-methylphenylsulfonyl-2-naphthoyldiazomethane, methylsulfonylbenzoyldiazomethane, t
Examples thereof include bissulfonyldiazomethane and sulfonylcarbonyldiazomethane such as ert-butoxycarbonyl-4-methylphenylsulfonyldiazomethane.

Examples of the N-sulfonyloxyimide type photoacid generator include succinimide, naphthalenedicarboxylic acid imide, phthalic acid imide, cyclohexyldicarboxylic acid imide, 5-norbornene-2,3-dicarboxylic acid imide, and 7-oxabicyclo. [2.2.1] -5-heptene-2,3-dicarboxylic acid imide imide skeleton and trifluoromethanesulfonate, nonafluorobutanesulfonate, heptadecafluorooctanesulfonate, 2,
2,2-trifluoroethane sulfonate, pentafluorobenzene sulfonate, 4-trifluoromethylbenzene sulfonate, 4-fluorobenzene sulfonate, toluene sulfonate, benzene sulfonate, naphthalene sulfonate, camphor sulfonate, octane sulfonate, dodecyl benzene sulfonate, butane sulfonate, A combination of compounds such as methanesulfonate may be mentioned.

As the benzoin sulfonate type photoacid generator, benzoin tosylate, benzoin mesylate,
Examples thereof include benzoin butane sulfonate.

Examples of the pyrogallol trisulfonate-type photoacid generator include pyrogallol, phloroglycine, catechol, resorcinol, and hydroquinone, all of which have trifluoromethanesulfonate, nonafluorobutanesulfonate, heptadecafluorooctanesulfonate, 2,2,2. -Trifluoroethane sulfonate, pentafluorobenzene sulfonate, 4-trifluoromethylbenzene sulfonate, 4-fluorobenzene sulfonate, toluene sulfonate, benzene sulfonate, naphthalene sulfonate, camphor sulfonate, octane sulfonate, dodecyl benzene sulfonate, butane sulfonate, methane sulfonate, etc. The compound substituted by is mentioned.

Examples of the nitrobenzyl sulfonate type photoacid generator include 2,4-dinitrobenzyl sulfonate and 2
-Nitrobenzyl sulfonate, 2,6-dinitrobenzyl sulfonate, and the sulfonate includes
Specifically, trifluoromethane sulfonate, nonafluorobutane sulfonate, heptadecafluorooctane sulfonate, 2,2,2-trifluoroethane sulfonate, pentafluorobenzene sulfonate, 4-trifluoromethylbenzene sulfonate, 4-fluorobenzene sulfonate, toluene sulfonate , Benzene sulfonate, naphthalene sulfonate, camphor sulfonate, octane sulfonate, dodecyl benzene sulfonate, butane sulfonate, methane sulfonate and the like. A compound in which the nitro group on the benzyl side is replaced with a trifluoromethyl group can also be used in the same manner.

Examples of the sulfone type photoacid generator include bis (phenylsulfonyl) methane, bis (4-methylphenylsulfonyl) methane, bis (2-naphthylsulfonyl) methane and 2,2-bis (phenylsulfonyl) propane. , 2,2-bis (4-methylphenylsulfonyl)
Propane, 2,2-bis (2-naphthylsulfonyl) propane, 2-methyl-2- (p-toluenesulfonyl)
Propiophenone, 2- (cyclohexylcarbonyl)
-2- (p-toluenesulfonyl) propane, 2,4-
Dimethyl-2- (p-toluenesulfonyl) pentane-
3-on and the like can be mentioned.

Examples of glyoxime derivative type photoacid generators include bis-o- (p-toluenesulfonyl) -α-
Dimethylglyoxime, bis-o- (p-toluenesulfol) -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- (t
ert-butanesulfonyl) -α-dimethylglyoxime, bis-o- (perfluorooctanesulfonyl)-
α-dimethylglyoxime, bis-o- (cyclohexylsulfonyl) -α-dimethylglyoxime, bis-o
-(Benzenesulfonyl) -α-dimethylglyoxime, bis-o- (p-fluorobenzenesulfonyl)-
α-dimethylglyoxime, bis-o- (p-tert
-Butylbenzenesulfonyl) -α-dimethylglyoxime, bis-o- (xylenesulfonyl) -α-dimethylglyoxime, bis-o- (camphorsulfonyl)
Examples include -α-dimethylglyoxime.

Among them, photoacid generators preferably used include sulfonium salts, bissulfonyldiazomethane,
It is N-sulfonyloxyimide.

The optimum anion of the generated acid differs depending on the ease of cleavage of the acid labile group used in the polymer, but generally, anion having no volatility or extremely high diffusibility is selected. Suitable anions in this case are benzenesulfonate anion, toluenesulfonate anion, 4- (4
-Toluenesulfonyloxy) benzenesulfonate anion, pentafluorobenzenesulfonate anion,
2,2,2-trifluoroethanesulfonic acid anion,
Nonafluorobutane sulfonate anion, heptadecafluorooctane sulfonate anion, and camphor sulfonate anion.

The addition amount of the photo-acid generator (C) in the chemically amplified positive resist composition of the present invention is 0.5 to 20 parts by weight, preferably 1 to 100 parts by weight of the base resin in the resist material. 10 parts by weight. The photoacid generator (C) may be used alone or in combination of two or more. Further, it is also possible to use a photo-acid generator having a low transmittance at the exposure wavelength and control the transmittance in the resist film by adjusting the amount added.

As the dissolution inhibitor of the component (D), a compound having a weight average molecular weight of 100 to 1,000 and having two or more phenolic hydroxyl groups in the molecule is acid-labile to the hydrogen atom of the phenolic hydroxyl group. Average 1 as a whole
A compound substituted at a ratio of 0 to 100 mol% is preferable.
The weight average molecular weight of the above compound is 100 to 1,000.
It is 0, preferably 150 to 800. The content of the dissolution inhibitor is 0 to 50 parts by weight, preferably 5 to 50 parts by weight, more preferably 10 to 100 parts by weight of the base resin.
It is 30 parts by weight and can be used alone or in combination of two or more kinds. If the blending amount is small, the resolution may not be improved in some cases, and if the blending amount is too large, the film thickness of the pattern may decrease and the resolution tends to decrease.

Examples of such a dissolution inhibitor of the component (D) which is preferably used are bis (4- (2'-tetrahydropyranyloxy) phenyl) methane and bis (4-
(2'-tetrahydrofuranyloxy) phenyl) methane, bis (4-tert-butoxyphenyl) methane,
Bis (4-tert-butoxycarbonyloxyphenyl) methane, bis (4-tert-butoxycarbonylmethyloxyphenyl) methane, bis (4- (1′-ethoxyethoxy) phenyl) methane, bis (4- (1 ′)
-Ethoxypropyloxy) phenyl) methane, 2,2
-Bis (4 '-(2''-tetrahydropyranyloxy)) propane, 2,2-bis (4'-(2 ''-tetrahydrofuranyloxy) phenyl) propane, 2,2
-Bis (4'-tert-butoxyphenyl) propane, 2,2-bis (4'-tert-butoxycarbonyloxyphenyl) propane, 2,2-bis (4-te
rt-Butoxycarbonylmethyloxyphenyl) propane, 2,2-bis (4 ′-(1 ″ -ethoxyethoxy) phenyl) propane, 2,2-bis (4′-
(1 ″ -Ethoxypropyloxy) phenyl) propane, 4,4-bis (4 ′-(2 ″ -tetrahydropyranyloxy) phenyl) tert-butylvalerate, 4,4
-Bis (4 '-(2''-tetrahydrofuranyloxy) phenyl) valerate tert-butyl, 4,4-bis (4'-tert-butoxyphenyl) valerate tert
Butyl, tert-butyl 4,4-bis (4-tert-butoxycarbonyloxyphenyl) valerate, 4,4-
Bis (4′-tert-butoxycarbonylmethyloxyphenyl) valerate tert-butyl, 4,4-bis (4 ′-(1 ″ -ethoxyethoxy) phenyl) valerate tert-butyl, 4,4-bis (4 ′) Tert-butyl- (1 ''-ethoxypropyloxy) phenyl) valerate, tris (4- (2'-tetrahydropyranyloxy) phenyl) methane, tris (4- (2'-tetrahydrofuranyloxy) phenyl) methane, Tris (4-
tert-butoxyphenyl) methane, tris (4-t
ert-butoxycarbonyloxyphenyl) methane,
Tris (4-tert-butoxycarbonyloxymethylphenyl) methane, tris (4- (1′-ethoxyethoxy) phenyl) methane, tris (4- (1′-ethoxypropyloxy) phenyl) methane, 1,1,2 −
Tris (4 ′-(2 ″ -tetrahydropyranyloxy) phenyl) ethane, 1,1,2-tris (4′-
(2 ″ -tetrahydrofuranyloxy) phenyl) ethane, 1,1,2-tris (4′-tert-butoxyphenyl) ethane, 1,1,2-tris (4′-ter
t-butoxycarbonyloxyphenyl) ethane, 1,
1,2-tris (4′-tert-butoxycarbonylmethyloxyphenyl) ethane, 1,1,2-tris (4 ′-(1′-ethoxyethoxy) phenyl) ethane, 1,1,2-tris (4 Examples include '-(1'-ethoxypropyloxy) phenyl) ethane and the like.

As the basic compound as the component (E), a compound which can suppress the diffusion rate when the acid generated from the photo-acid generator diffuses in the resist film is suitable. With the combination of, the acid diffusion rate in the resist film is suppressed and the resolution is improved, the sensitivity change after exposure is suppressed, the dependency on the substrate and the environment is reduced, and the exposure margin and pattern profile are improved. can do.

Examples of the basic compound as the component (E) include primary, secondary and tertiary aliphatic amines, mixed amines, aromatic amines, heterocyclic amines and carboxy groups. And a nitrogen-containing compound having a sulfonyl group, a nitrogen-containing compound having a hydroxy group, a nitrogen-containing compound having a hydroxyphenyl group, an alcoholic nitrogen-containing compound, an amide derivative, an imide derivative and the like.

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

Examples of the mixed amines include dimethylethylamine, methylethylpropylamine, benzylamine, phenethylamine, benzyldimethylamine and the like. Specific examples of aromatic amines and heterocyclic amines include aniline derivatives (eg, aniline, N-methylaniline, N-ethylaniline, N-propylaniline, N, N-dimethylaniline, 2-methylaniline, 3 -Melaniline, 4-methylaniline,
Ethylaniline, propylaniline, trimethylaniline, 2-nitroaniline, 3-nitroaniline, 4-nitroaniline, 2,4-dinitroaniline, 2,6-dinitroaniline, 3,5-dinitroaniline, N, N-
Dimethyltoluidine), diphenyl (p-tolyl) amine, methyldiphenylamine, triphenylamine,
Phenylenediamine, naphthylamine, diaminonaphthalene, pyrrole derivative (for example, pyrrole, 2H-pyrrole, 1-methylpyrrole, 2,4-dimethylpyrrole, 2,5-dimethylpyrrole, N-methylpyrrole, etc.), oxazole derivative (for example, Oxazole, isoxazole etc.), thiazole derivative (eg thiazole, isothiazole etc.), imidazole derivative (eg imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole etc.), pyrazole derivative, furazan derivative, pyrroline derivative (Eg, pyrroline, 2-methyl-1-pyrroline, etc.), pyrrolidine derivative (eg, pyrrolidine, N-methylpyrrolidine, pyrrolidinone, N-methylpyrrolidone, etc.), imidazoline derivative, imidazolidine derivative Body, pyridine derivatives (for example,
Pyridine, methylpyridine, ethylpyridine, propylpyridine, butylpyridine, 4- (1-butylpentyl) pyridine, dimethylpyridine, trimethylpyridine, triethylpyridine, phenylpyridine, 3-methyl-2-phenylpyridine, 4-tert-butyl. Pyridine, diphenylpyridine, benzylpyridine, methoxypyridine, butoxypyridine, dimethoxypyridine,
1-methyl-2-pyridine, 4-pyrrolidinopyridine,
1-methyl-4-phenylpyridine, 2- (1-ethylpropyl) pyridine, aminopyridine, dimethylaminopyridine, etc.), pyridazine derivative, pyrimidine derivative,
Pyrazine derivative, pyrazoline derivative, pyrazolidine derivative, piperidine derivative, piperazine derivative, morpholine derivative, indole derivative, isoindole derivative, 1
H-indazole derivative, indoline derivative, quinoline derivative (eg, quinoline, 3-quinolinecarbonitrile, etc.), isoquinoline derivative, cinnoline derivative, quinazoline derivative, quinoxaline derivative, phthalazine derivative, purine derivative, pteridine derivative, carbazole derivative, phenanthridine Derivative, acridine derivative, phenazine derivative, 1,10-phenanthroline derivative,
Adenine derivative, adenosine derivative, guanine derivative,
Examples include guanosine derivatives, uracil derivatives, uridine derivatives and the like.

Further, examples of the nitrogen-containing compound having a carboxyl group include aminobenzoic acid, indolecarboxylic acid, amino acid derivatives (eg, nicotinic acid, alanine, arginine, aspartic acid, glutamic acid, glycine, histidine, isoleucine, glycyl). Leucine,
Leucine, methionine, phenylalanine, threonine, lysine, 3-aminopyrazine-2-carboxylic acid, methoxyalanine, etc.) are exemplified, and as the nitrogen-containing compound having a sulfonyl group, 3-pyridinesulfonic acid, p
-Pyridinium toluenesulfonate and the like are exemplified, and as the nitrogen-containing compound having a hydroxy group, the nitrogen-containing compound having a hydroxyphenyl group, and the alcoholic nitrogen-containing compound, 2-hydroxypyridine, aminocresol,
2,4-quinoline diol, 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, piperidine ethanol, 1- (2-hydroxyethyl) pyrrolidine, 1- (2-hydroxyethyl) -2-
Pyrrolidinone, 3-piperidino-1,2-propanediol, 3-pyrrolidino-1,2-propanediol, 8
-Hydroxyjulolidine, 3-cuinclidinol, 3
-Tropanol, 1-methyl-2-pyrrolidine ethanol, 1-aziridine ethanol, N- (2-hydroxyethyl) phthalimide, N- (2-hydroxyethyl)
Isonicotinamide and the like are exemplified. As the amide derivative, formamide, N-methylformamide, N, N
-Dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide and the like are exemplified. Examples of the imide derivative include phthalimide, succinimide, and maleimide.

Furthermore, one or more selected from the basic compounds represented by the following general formula (B) -1 can be added. N (X) _n (Y) _3-n (B) -1 In the formula, 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.

[0104]

[Chemical 32]

The side chain Y represents the same or different hydrogen atom or a linear, branched or cyclic C1-C20 alkyl group, and may contain an ether group or a hydroxyl group. In addition, Xs may combine with each other to form a ring.

Here, R ³⁰⁰ , R ³⁰² and R ³⁰⁵ have 1 carbon atom.
~ 4 linear or branched alkylene group, R
³⁰¹ and R ³⁰⁴ are a hydrogen atom or a straight chain having 1 to 20 carbon atoms,
It is a branched or cyclic alkyl group and may contain one or more hydroxy groups, ether groups, ester groups, and lactone rings.

R ³⁰³ is a single bond and is a linear or branched alkylene group having 1 to 4 carbon atoms, and R ³⁰⁶ is 1 carbon atom.
To 20 linear, branched or cyclic alkyl groups, which may contain one or more hydroxy groups, ether groups, ester groups and lactone rings.

Specific examples of the compound represented by formula (B) -1 are shown 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 [8.8.8] hexacosane, 4,7,13,18-tetraoxa-1,10-
Diazabicyclo [8.5.5] eicosane, 1,4,1
0,13-tetraoxa-7,16-diazabicyclooctadecane, 1-aza-12-crown-4, 1-aza-15-crown-5, 1-aza-18-crown-
6, tris (2-formyloxyethyl) amine, tris (2-formyloxyethyl) amine, tris (2
-Acetoxyethyl) amine, tris (2-propionyloxyethyl) amine, tris (2-butyryloxyethyl) amine, tris (2-isobutyryloxyethyl) amine, tris (2-valeryloxyethyl) amine, Tris (2-pivaloyloxyxyethyl) amine, N, N-bis (2-acetoxyethyl) 2- (acetoxyacetoxy) ethylamine, tris (2-methoxycarbonyloxyethyl) amine, tris (2-te
rt-Butoxycarbonyloxyethyl) amine, tris [2- (2-oxopropoxy) ethyl] amine, tris [2- (methoxycarbonylmethyl) oxyethyl] amine, tris [2- (tert-butoxycarbonylmethyloxy) ethyl] Amine, tris [2- (cyclohexyloxycarbonylmethyloxy) ethyl]
Amine, tris (2-methoxycarbonylethyl) amine, tris (2-ethoxycarbonylethyl) amine,
N, N-bis (2-hydroxyethyl) 2- (methoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (methoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2 -(Ethoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (ethoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2- (2
-Methoxyethoxycarbonyl) ethylamine, N, N
-Bis (2-acetoxyethyl) 2- (2-methoxyethoxycarbonyl) ethylamine, N, N-bis (2-
Hydroxyethyl) 2- (2-hydroxyethoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (2-acetoxyethoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2
-[(Methoxycarbonyl) methoxycarbonyl] ethylamine, N, N-bis (2-acetoxyethyl) 2-
[(Methoxycarbonyl) methoxycarbonyl] ethylamine, N, N-bis (2-hydroxyethyl) 2-
(2-oxopropoxycarbonyl) ethylamine,
N, N-bis (2-acetoxyethyl) 2- (2-oxopropoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2- (tetrahydrofurfuryloxycarbonyl) ethylamine, N, N-bis ( Two
-Acetoxyethyl) 2- (tetrahydrofurfuryloxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2-[(2-oxotetrahydrofuran-3-yl) oxycarbonyl] ethylamine, N,
N-bis (2-acetoxyethyl) 2-[(2-oxotetrahydrofuran-3-yl) oxycarbonyl] ethylamine, N, N-bis (2-hydroxyethyl) 2
-(4-Hydroxybutoxycarbonyl) ethylamine, N, N-bis (2-formyloxyethyl) 2-
(4-formyloxybutoxycarbonyl) ethylamine, N, N-bis (2-formyloxyethyl) 2-
(2-Formyloxyethoxycarbonyl) ethylamine, N, N-bis (2-methoxyethyl) 2- (methoxycarbonyl) ethylamine, N- (2-hydroxyethyl) bis [2- (methoxycarbonyl) ethyl] amine, N -(2-acetoxyethyl) bis [2- (methoxycarbonyl) ethyl] amine, N- (2-hydroxyethyl) bis [2- (ethoxycarbonyl) ethyl] amine, N- (2-acetoxyethyl) bis [2 -(Ethoxycarbonyl) ethyl] amine, N- (3-hydroxy-1-propyl) bis [2- (methoxycarbonyl)
Ethyl] amine, N- (3-acetoxy-1-propyl) bis [2- (methoxycarbonyl) ethyl] amine, N- (2-methoxyethyl) bis [2- (methoxycarbonyl) ethyl] amine, N-butylbis [2-
(Methoxycarbonyl) ethyl] amine, N-butylbis [2- (2-methoxyethoxycarbonyl) ethyl]
Amine, N-methylbis (2-acetoxyethyl) amine, N-ethylbis (2-acetoxyethyl) amine,
N-methylbis (2-pivaloyloxyxyethyl) amine, N-ethylbis [2- (methoxycarbonyloxy) ethyl] amine, N-ethylbis [2- (tert.
-Butoxycarbonyloxy) ethyl] amine, tris (methoxycarbonylmethyl) amine, tris (ethoxycarbonylmethyl) amine, N-butylbis (methoxycarbonylmethyl) amine, N-hexylbis (methoxycarbonylmethyl) amine, β- (diethylamino) Examples thereof include, but are not limited to, -δ-valerolactone.

Further, one or more basic compounds having a cyclic structure represented by the following general formula (B) -2 can be added.

[0110]

[Chemical 33] (In the formula, X is as described above, R ³⁰⁷ is a linear or branched alkylene group having 2 to 20 carbon atoms, and contains one or more of a carbonyl group, an ether group, an ester group, and a sulfide. Good too.)

Specifically, as the formula (B) -2, 1- [2
-(Methoxymethoxy) ethyl] pyrrolidine, 1- [2
-(Methoxymethoxy) ethyl] piperidine, 4- [2
-(Methoxymethoxy) ethyl] morpholine, 1- [2
-[(2-methoxyethoxy) methoxy] ethyl] pyrrolidine, 1- [2-[(2-methoxyethoxy) methoxy] ethyl] piperidine, 4- [2-[(2-methoxyethoxy) methoxy] ethyl] morpholine, Acetic acid 2-
(1-pyrrolidinyl) ethyl, 2-piperidinoethyl acetate, 2-morpholinoethyl acetate, 2- (1-pyrrolidinyl) ethyl formate, 2-piperidinoethyl propionate,
Acetoxyacetic acid 2-morpholinoethyl, methoxyacetic acid 2
-(1-Pyrrolidinyl) ethyl, 4- [2- (methoxycarbonyloxy) ethyl] morpholine, 1- [2-
(T-Butoxycarbonyloxy) ethyl] piperidine, 4- [2- (2-methoxyethoxycarbonyloxy) ethyl] morpholine, methyl 3- (1-pyrrolidinyl) propionate, methyl 3-piperidinopropionate, 3- Methyl morpholino propionate, methyl 3- (thiomorpholino) propionate, 2-methyl-3- (1
-Methyl pyrrolidinyl) propionate, ethyl 3-morpholinopropionate, methoxycarbonylmethyl 3-piperidinopropionate, 2-hydroxyethyl 3- (1-pyrrolidinyl) propionate, 2-acetoxyethyl 3-morpholinopropionate, 3 -(1-Pyrrolidinyl) propionic acid 2-oxotetrahydrofuran-3-
Yl, tetrahydrofurfuryl 3-morpholinopropionate, glycidyl 3-piperidinopropionate, 2-methoxyethyl 3-morpholinopropionate, 3- (1-
2- (2-methoxyethoxy) ethyl pyrrolidinyl) propionate, butyl 3-morpholinopropionate, 3-
Cyclohexyl piperidinopropionate, α- (1-pyrrolidinyl) methyl-γ-butyrolactone, β-piperidino-γ-butyrolactone, β-morpholino-δ-valerolactone, methyl 1-pyrrolidinyl acetate, methyl piperidinoacetate, methyl morpholinoacetate , Methyl thiomorpholino acetate, ethyl 1-pyrrolidinyl acetate, and 2-methoxyethyl morpholino acetate.

Further, a basic compound containing a cyano group represented by formulas (B) -3 to (B) -6 can be added.

[0113]

[Chemical 34] (In the formula, X, R ³⁰⁷ , and n are as described above, and R ³⁰⁸ and R ³⁰⁹ are the same or different and are linear or branched alkylene groups having 1 to 4 carbon atoms.)

The base containing a cyano group is specifically 3-
(Diethylamino) propiononitrile, N, N-bis (2-hydroxyethyl) -3-aminopropiononitrile, N, N-bis (2-acetoxyethyl) -3-aminopropiononitrile, N, N-bis (2-formyloxyethyl) -3-aminopropiononitrile, N,
N-bis (2-methoxyethyl) -3-aminopropiononitrile, N, N-bis [2- (methoxymethoxy)
Ethyl] -3-aminopropiononitrile, N- (2-
Cyanoethyl) -N- (2-methoxyethyl) -3-methylaminopropionate, N- (2-cyanoethyl)-
Methyl N- (2-hydroxyethyl) -3-aminopropionate, N- (2-acetoxyethyl) -N- (2-
Methyl cyanoethyl) -3-aminopropionate, N-
(2-Cyanoethyl) -N-ethyl-3-aminopropiononitrile, N- (2-cyanoethyl) -N- (2-
Hydroxyethyl) -3-aminopropiononitrile,
N- (2-acetoxyethyl) -N- (2-cyanoethyl) -3-aminopropiononitrile, N- (2-cyanoethyl) -N- (2-formyloxyethyl) -3-
Aminopropiononitrile, N- (2-cyanoethyl)
-N- (2-methoxyethyl) -3-aminopropiononitrile, N- (2-cyanoethyl) -N- [2- (methoxymethoxy) ethyl] -3-aminopropiononitrile, N- (2-cyanoethyl) ) -N- (3-Hydroxy-1-propyl) -3-aminopropiononitrile,
N- (3-acetoxy-1-propyl) -N- (2-cyanoethyl) -3-aminopropiononitrile, N-
(2-Cyanoethyl) -N- (3-formyloxy-1
-Propyl) -3-aminopropiononitrile, N-
(2-Cyanoethyl) -N-tetrahydrofurfuryl-
3-aminopropiononitrile, N, N-bis (2-cyanoethyl) -3-aminopropiononitrile, diethylaminoacetonitrile, N, N-bis (2-hydroxyethyl) aminoacetonitrile, N, N-bis (2-
Acetoxyethyl) aminoacetonitrile, N, N-bis (2-formyloxyethyl) aminoacetonitrile, N, N-bis (2-methoxyethyl) aminoacetonitrile, N, N-bis [2- (methoxymethoxy) ethyl] amino Acetonitrile, N-cyanomethyl-N-
Methyl (2-methoxyethyl) -3-aminopropionate, N-cyanomethyl-N- (2-hydroxyethyl)
Methyl-3-aminopropionate, N- (2-acetoxyethyl) -N-cyanomethyl-3-aminopropionate methyl, N-cyanomethyl-N- (2-hydroxyethyl) aminoacetonitrile, N- (2-acetoxyethyl) ) -N- (cyanomethyl) aminoacetonitrile,
N-cyanomethyl-N- (2-formyloxyethyl)
Aminoacetonitrile, N-cyanomethyl-N- (2-
Methoxyethyl) aminoacetonitrile, N-cyanomethyl-N- [2- (methoxymethoxy) ethyl] aminoacetonitrile, N- (cyanomethyl) -N- (3-hydroxy-1-propyl) aminoacetonitrile, N-
(3-acetoxy-1-propyl) -N- (cyanomethyl) aminoacetonitrile, N-cyanomethyl-N-
(3-formyloxy-1-propyl) aminoacetonitrile, N, N-bis (cyanomethyl) aminoacetonitrile, 1-pyrrolidinepropiononitrile, 1-piperidinepropiononitrile, 4-morpholinepropiononitrile, 1-pyrrolidineacetonitrile, 1-piperidine acetonitrile, 4-morpholine acetonitrile,
Cyanomethyl 3-diethylaminopropionate, N, N
-Bis (2-hydroxyethyl) -3-aminopropionate cyanomethyl, N, N-bis (2-acetoxyethyl) -3-aminopropionate cyanomethyl, N, N-
Bis (2-formyloxyethyl) -3-aminopropionate cyanomethyl, N, N-bis (2-methoxyethyl) -3-aminopropionate cyanomethyl, N, N-
Bis [2- (methoxymethoxy) ethyl] -3-aminopropionic acid cyanomethyl, 3-diethylaminopropionic acid (2-cyanoethyl), N, N-bis (2-hydroxyethyl) -3-aminopropionic acid (2-cyanoethyl) ), N, N-bis (2-acetoxyethyl) -3
-Aminopropionic acid (2-cyanoethyl), N, N-
Bis (2-formyloxyethyl) -3-aminopropionic acid (2-cyanoethyl), N, N-bis (2-methoxyethyl) -3-aminopropionic acid (2-cyanoethyl), N, N-bis [2 -(Methoxymethoxy) ethyl] -3-aminopropionic acid (2-cyanoethyl),
1-Pyrrolidine propionate cyanomethyl, 1-piperidine propionate cyanomethyl, 4-morpholine cyanomethyl propionate, 1-pyrrolidine propionate (2
-Cyanoethyl), 1-piperidinepropionic acid (2-
Examples are cyanoethyl) and 4-morpholinepropionic acid (2-cyanoethyl).

The basic compound of the present invention is incorporated in an amount of 0.001 to 2 parts by weight based on 100 parts by weight of the total base resin.
Particularly, 0.01 to 1 part by weight is suitable. Compounding amount 0.0
If it is less than 01 parts by weight, the compounding effect may not be obtained, and if it exceeds 2 parts by weight, the sensitivity may be lowered too much.

A surfactant for improving the coating property can be further added to the chemically amplified positive resist composition of the present invention.

Examples of the surface active agent include, but are not limited to, polyoxyethylene lauryl ether, polyoxyethylene steryl ether, polyoxyethylene cetyl ether, polyoxyethylene olein ether, and other polyoxyethylene alkyls. Ethers, polyoxyethylene octylphenol ether,
Polyoxyethylene alkyl allylic ethers such as polyoxyethylene nonylphenol ether, polyoxyethylene polyoxypropylene block copolymers,
Sorbitan monolaurate, sorbitan monopalmitate, sorbitan fatty acid esters such as sorbitan monostearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate,
Nonionic surfactants of polyoxyethylene sorbitan fatty acid ester such as polyoxyethylene sorbitan trioleate and polyoxyethylene sorbitan tristearate, Ftop EF301, EF303, EF35
2 (Tochem Products), Megafac F171, F
172, F173 (Dainippon Ink and Chemicals), Florard FC430, FC431 (Sumitomo 3M), Asahi Guard AG710, Surflon S-381, S-38
2, SC101, SC102, SC103, SC10
4, SC105, SC106, Surfynol E100
4, KH-10, KH-20, KH-30, KH-40
(Asahi Glass) and other fluorine-containing surfactants, organosiloxane polymer KP341, X-70-092, X-70-
093 (Shin-Etsu Chemical Co., Ltd.), acrylic acid-based or methacrylic acid-based Polyflow No. 75, No. 95 (Kyoeisha Yushi Kagaku Kogyo), among them FC430, Surflon S
-381, Surfynol E1004, KH-20, K
H-30 is preferred. These can be used alone or in combination of two or more.

The addition amount of the surfactant in the chemically amplified positive resist composition of the present invention is 2 parts by weight or less, preferably 1 part by weight or less, relative to 100 parts by weight of the base resin in the resist material composition. .

A chemically amplified positive type composition containing (A) the organic solvent of the present invention, (B) the polymer compound represented by the above general formulas (1), (2) and (3), and (C) an acid generator. When the resist material is used for manufacturing various integrated circuits, a known lithography technique can be used, although not particularly limited thereto.

Substrates for manufacturing integrated circuits (Si, SiO ₂ ,
SiN, SiON, TiN, WSi, BPSG, SO
G, organic antireflective film, various LowK materials, etc.) by a suitable coating method such as spin coating, roll coating, flow coating, dip coating, spray coating, doctor coating, and nozzle scanning. 0.0μ
m so that it becomes 60 to 15 on a hot plate.
0 ° C, 1 to 10 minutes, preferably 80 to 120 ° C, 1 to
Pre-bake for 5 minutes. Then, the desired pattern is exposed through a predetermined mask with a light source selected from ultraviolet rays, far ultraviolet rays, vacuum ultraviolet rays, electron beams, X-rays, excimer lasers, γ rays, synchrotron radiation, etc., preferably with an exposure wavelength of 300 nm or less. To do. Exposure amount is 1 ~ 200mJ
/ Cm ² , preferably 1 to 100 mJ / cm ² about. 60 ~ 180 ℃ on a hot plate, 10 seconds ~ 5 minutes, preferably 80 ~
Post exposure bake (PEB) at 150 ° C. for 30 seconds to 3 minutes.

Further, 0.1 to 5%, preferably 1 to 3%
Using a developer of an aqueous alkaline solution such as tetramethylammonium hydroxide (TMAH) for 10 seconds to 3 minutes, preferably 20 seconds to 2 minutes, dipping method, paddle method, spray method, etc. Then, the target pattern is formed on the substrate by developing in the usual manner. In addition, the resist material of the present invention is particularly suitable for deep ultraviolet rays of 254 to 193 nm among high energy rays, and
It is most suitable for fine patterning by vacuum ultraviolet ray of 57 nm, electron beam, soft X-ray, X-ray, excimer laser, γ-ray and synchrotron radiation. If the above range falls outside the upper and lower limits, the desired pattern may not be obtained.

[0122]

Industrial Applicability The resist material of the present invention has a significantly high alkali dissolution rate contrast before and after exposure, has high sensitivity and high resolution, and exhibits particularly excellent etching resistance. It is possible to provide a resist material such as a chemically amplified resist material suitable as the fine pattern forming material.

[0123]

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

[Synthesis Example 1] 13.2 g of acetoxystyrene, 59.1 g of indole, 8.0 g of 1-ethylcyclopentyl methacrylate and 80 g of toluene as a solvent were added to a 2 L flask. This reaction vessel was cooled to −70 ° C. under a nitrogen atmosphere, and deaeration under reduced pressure and nitrogen blowing were repeated 3 times. After heating to room temperature, AIB as a polymerization initiator
4.1 g of N (azobisisobutyronitrile) was added, and 6
After raising the temperature to 0 ° C., the reaction was carried out for 15 hours. The reaction solution was concentrated to 1/2, precipitated in a mixed solution of 4.5 L of methanol and 0.5 L of water, and the obtained white solid was filtered and
It was dried under reduced pressure at 0 ° C. to obtain 63 g of a white polymer. This polymer was added with 0.5 L of methanol and 1.0 of tetrahydrofuran.
It was redissolved in L, 70 g of triethylamine and 15 g of water were added, a deprotection reaction was carried out, and the mixture was neutralized with acetic acid. The reaction solution was concentrated, dissolved in 0.5 L of acetone, and subjected to the same precipitation, filtration and drying as above to obtain 55 g of a white polymer.

The obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, and the following analysis results were obtained. Copolymerization composition ratio hydroxystyrene: indole: 1-ethylcyclopentyl methacrylate = 58.8: 23.5: 17.7 Weight average molecular weight (Mw) = 12,800 Molecular weight distribution (Mw / Mn) = 1.88 (Polymer 1).

[Synthesis Example 2] 13.3 g of acetoxystyrene and 59.6 of 2,3-benzofuran were placed in a 2 L flask.
g, 1-ethylcyclopentyl methacrylate 8.0 g,
80 g of toluene was added as a solvent. This reaction vessel was cooled to −70 ° C. under a nitrogen atmosphere, and deaeration under reduced pressure and nitrogen blowing were repeated 3 times. After warming to room temperature, 4.1 g of AIBN as a polymerization initiator was added, and after warming to 60 ° C., 15
Reacted for hours. The reaction solution was concentrated to 1/2 and precipitated in a mixed solution of 4.5 L of methanol and 0.5 L of water, and the obtained white solid was filtered and dried under reduced pressure at 60 ° C.
66 g of a white polymer was obtained. This polymer was redissolved in 0.5 L of methanol and 1.0 L of tetrahydrofuran,
70 g of triethylamine and 15 g of water were added, a deprotection reaction was performed, and the mixture was neutralized with acetic acid. The reaction solution was concentrated and then dissolved in 0.5 L of acetone, and the same precipitation, filtration and drying as above were carried out to obtain 58 g of a white polymer.

The polymer obtained was subjected to ¹³ C, ¹ H-NMR and GPC measurements, and the following analysis results were obtained. Copolymerization composition ratio Hydroxystyrene: 2,3-benzofuran: 1-ethylcyclopentyl methacrylate = 57.0: 20.5:
22.5 Weight average molecular weight (Mw) = 11,200 Molecular weight distribution (Mw / Mn) = 1.91 This is designated as (Polymer 2).

[Synthesis Example 3] 13.2 g of acetoxystyrene and 67.7 of benzo [b] thiophene were placed in a 2 L flask.
g, 1-ethylcyclopentyl methacrylate 8.0 g,
80 g of toluene was added as a solvent. This reaction vessel was cooled to −70 ° C. under a nitrogen atmosphere, and deaeration under reduced pressure and nitrogen blowing were repeated 3 times. After warming to room temperature, 4.1 g of AIBN as a polymerization initiator was added, and after warming to 60 ° C., 15
Reacted for hours. The reaction solution was concentrated to 1/2 and precipitated in a mixed solution of 4.5 L of methanol and 0.5 L of water, and the obtained white solid was filtered and dried under reduced pressure at 60 ° C.
61 g of a white polymer was obtained. This polymer was redissolved in 0.5 L of methanol and 1.0 L of tetrahydrofuran,
70 g of triethylamine and 15 g of water were added, a deprotection reaction was performed, and the mixture was neutralized with acetic acid. The reaction solution was concentrated, dissolved in 0.5 L of acetone, and subjected to the same precipitation, filtration and drying as above to obtain 53 g of a white polymer.

The polymer obtained was subjected to ¹³ C, ¹ H-NMR and GPC measurements, and the following analysis results were obtained. Copolymerization composition ratio Hydroxystyrene: 2,3-benzofuran: 1-ethylcyclopentyl methacrylate = 54.7: 18.2:
27.1 Weight average molecular weight (Mw) = 1,500 Molecular weight distribution (Mw / Mn) = 1.62 This is designated as (Polymer 3).

[Synthesis Example 4] 13.2 g of acetoxystyrene, 58.6 g of indene, 59.1 g of indole, 8.0 g of 1-ethylcyclopentyl methacrylate and 80 g of toluene as a solvent were added to a 2 L flask. This reaction vessel was cooled to −70 ° C. under a nitrogen atmosphere, and deaeration under reduced pressure and nitrogen blowing were repeated 3 times. After the temperature was raised to room temperature, 4.1 g of AIBN (azobisisobutyronitrile) was added as a polymerization initiator, the temperature was raised to 60 ° C., and the reaction was performed for 15 hours. The reaction solution was concentrated to 1/2, precipitated in a mixed solution of 4.5 L of methanol and 0.5 L of water, and the obtained white solid was filtered and dried under reduced pressure at 60 ° C. to obtain 88 g of a white polymer. It was This polymer was dissolved again in 0.5 L of methanol and 1.0 L of tetrahydrofuran, 70 g of triethylamine and 15 g of water were added, a deprotection reaction was performed, and the mixture was neutralized with acetic acid. After concentrating the reaction solution, acetone 0.5
After dissolving in L, the same precipitation, filtration and drying as above were carried out to obtain 75 g of a white polymer.

The polymer obtained was subjected to ¹³ C, ¹ H-NMR and GPC measurements, and the following analysis results were obtained. Copolymerization composition ratio hydroxystyrene: indene: indole: 1-ethylcyclopentyl methacrylate = 30.3: 28.5:
23.5: 17.7 Weight average molecular weight (Mw) = 7,800 Molecular weight distribution (Mw / Mn) = 1.82 This is designated as (polymer 4).

[Synthesis Example 5] To a 2 L flask, 13.3 g of acetoxystyrene, 58.6 g of indene, 59.6 g of 2,3-benzofuran, 8.0 g of 1-ethylcyclopentyl methacrylate and 80 g of toluene as a solvent were added. This reaction vessel was cooled to −70 ° C. under a nitrogen atmosphere, and deaeration under reduced pressure and nitrogen blowing were repeated 3 times. After warming to room temperature, 4.1 g of AIBN as a polymerization initiator was added,
After raising the temperature to 0 ° C., the reaction was carried out for 15 hours. The reaction solution was concentrated to 1/2, precipitated in a mixed solution of 4.5 L of methanol and 0.5 L of water, and the obtained white solid was filtered and
After drying under reduced pressure at 0 ° C., 90 g of a white polymer was obtained. This polymer was added with 0.5 L of methanol and 1.0 of tetrahydrofuran.
It was redissolved in L, 70 g of triethylamine and 15 g of water were added, a deprotection reaction was carried out, and the mixture was neutralized with acetic acid. The reaction solution was concentrated, dissolved in 0.5 L of acetone, and subjected to the same precipitation, filtration and drying as above to obtain 81 g of a white polymer.

The obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, and the following analysis results were obtained. Copolymerization composition ratio hydroxystyrene: indene: 2,3-benzofuran: 1-ethylcyclopentyl methacrylate = 28.
5: 28.5: 20.5: 22.5 Weight average molecular weight (Mw) = 7,200 Molecular weight distribution (Mw / Mn) = 1.88 This is referred to as (Polymer 5).

[Synthesis Example 6] In a 2 L flask, 13.3 g of acetoxystyrene, 58.6 g of indene, 67.7 g of benzo [b] thiophene, 8.0 g of 1-ethylcyclopentyl methacrylate, and 80 g of toluene as a solvent.
Was added. This reaction vessel was cooled to −70 ° C. under a nitrogen atmosphere, and deaeration under reduced pressure and nitrogen blowing were repeated 3 times. After the temperature was raised to room temperature, 4.1 g of AIBN was added as a polymerization initiator, the temperature was raised to 60 ° C., and the reaction was carried out for 15 hours. The reaction solution was concentrated to 1/2, methanol 4.5 L, water 0.
The white solid obtained was precipitated in 5 L of a mixed solution, filtered and dried under reduced pressure at 60 ° C. to obtain 95 g of a white polymer. This polymer was redissolved in 0.5 L of methanol and 1.0 L of tetrahydrofuran, and 70 g of triethylamine and 1
5 g was added, a deprotection reaction was performed, and the mixture was neutralized with acetic acid. The reaction solution was concentrated, dissolved in 0.5 L of acetone, and subjected to the same precipitation, filtration and drying as above to obtain 78 g of a white polymer.
Got

The obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, and the following analysis results were obtained. Copolymerization composition ratio hydroxystyrene: indene: 2,3-benzofuran: 1-ethylcyclopentyl methacrylate = 26.
5: 28.2: 18.2: 27.1 Weight average molecular weight (Mw) = 8,500 Molecular weight distribution (Mw / Mn) = 1.65 This is designated as (Polymer 6).

[Synthesis Example 7] 24.2 g of 4-acetoxystyrene and 3 of 6-acetoxyindene were placed in a 2 L flask.
5.2 g, 2,3-benzofuran 28.8 g, and 80 g of toluene as a solvent were added. This reaction vessel was cooled to −70 ° C. under a nitrogen atmosphere, deaerated under reduced pressure, and blown with nitrogen 3 times.
Repeated times. After heating to room temperature, AI as a polymerization initiator
4.1 g of BN was added, the temperature was raised to 60 ° C., and the reaction was performed for 15 hours. The reaction solution was concentrated to 1/2 and precipitated in a mixed solution of 4.5 L of methanol and 0.5 L of water, and the obtained white solid was filtered and dried under reduced pressure at 60 ° C. to obtain 75 g of a white polymer. It was This polymer was dissolved again in 0.5 L of methanol and 1.0 L of tetrahydrofuran, 70 g of triethylamine and 15 g of water were added, a deprotection reaction was performed, and the mixture was neutralized with acetic acid. After concentrating the reaction solution, acetone 0.5
After dissolving in L, the same precipitation, filtration and drying as above were carried out to obtain 65 g of a white polymer.

The polymer obtained was subjected to ¹³ C, ¹ H-NMR and GPC measurements, and the following analysis results were obtained. Copolymerization composition ratio 4-hydroxystyrene: 6-hydroxyindene:
2,3-benzofuran = 36.2: 33.5: 30.3 Weight average molecular weight (Mw) = 4,600 Molecular weight distribution (Mw / Mn) = 1.65 This is referred to as (polymer 7).

[Synthesis Example 8] 40 g of the above polymer 4 was added to 400 mL of tetrahydrofuran in a 2 L flask.
Dissolved in water, 0.7 g of methanesulfonic acid and 6.3 g of ethyl vinyl ether were added and reacted at room temperature for 1 hour, 1.2 g of aqueous ammonia (30%) was added to stop the reaction, and the reaction solution was added with 5 L of acetic acid water. Was crystallized and precipitated, and washed twice with water. The obtained white solid was filtered and dried under reduced pressure at 40 ° C. to obtain 42 g of a white polymer. The resulting polymer
^{When 13} C, ¹ H-NMR and GPC measurements were performed, the following analysis results were obtained. Copolymerization composition ratio Hydroxystyrene: p-ethoxyethoxystyrene:
6-hydroxyindene: 6-ethoxyethoxyindene: 2,3-benzofuran = 30.8: 5.4: 28.
5: 5.0: 30.3 Weight average molecular weight (Mw) = 4,920 Molecular weight distribution (Mw / Mn) = 1.65 This is designated as (polymer 8).

[Synthesis Example 9] To a 2 L flask were added 48.8 g of 6-acetoxyindene, 49.3 g of 6-acetoxy-2,3-benzofuran, and 80 g of toluene as a solvent. This reaction vessel was cooled to −70 ° C. under a nitrogen atmosphere, and deaeration under reduced pressure and nitrogen blowing were repeated 3 times. After heating to room temperature, 4.1 g of sulfuric acid as a polymerization initiator was added,
After the temperature was raised to ° C, the reaction was carried out for 15 hours. 1 of this reaction solution
The mixture was concentrated to 1/2 and precipitated in a mixed solution of 4.5 L of methanol and 0.5 L of water, and the obtained white solid was filtered, then 60
After drying under reduced pressure at ℃, 85 g of a white polymer was obtained. 0.5 L of this polymer and 1.0 L of tetrahydrofuran
Was redissolved in water, 70 g of triethylamine and 15 g of water were added, a deprotection reaction was performed, and the mixture was neutralized with acetic acid. The reaction solution was concentrated and then dissolved in 0.5 L of acetone, followed by the same precipitation, filtration and drying as above to obtain 65 g of a white polymer.

The polymer obtained was subjected to ¹³ C, ¹ H-NMR and GPC measurements, and the following analysis results were obtained. Copolymerization composition ratio 6-hydroxyindene: 6-hydroxy-2,3-benzofuran 50:50 Weight average molecular weight (Mw) = 4,100 Molecular weight distribution (Mw / Mn) = 1.45 This is referred to as (polymer 9). .

[Synthesis Example 10] Using a 2 L flask,
40 g of the above polymer 9 is added to tetrahydrofuran 400 m
Dissolve in L, add 1.4 g of methanesulfonic acid and 12.3 g of ethyl vinyl ether, react at room temperature for 1 hour, add 2.5 g of ammonia water (30%) to stop the reaction,
This reaction solution was crystallized and precipitated using 5 L of acetic acid water, washed twice with water, and the obtained white solid was filtered and then cooled to 40 ° C.
After drying under reduced pressure, 47 g of a white polymer was obtained.

The obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, and the following analysis results were obtained. Copolymerization composition ratio 6-hydroxyindene: 6-ethoxyethoxyindene: 6-hydroxy-2,3-benzofuran: 6-ethoxyethoxy-2,3-benzofuran = 37.5: 1
2.5: 37.5: 12.5 Weight average molecular weight (Mw) = 4,300 Molecular weight distribution (Mw / Mn) = 1.45 This is designated as (Polymer 10).

[Synthesis Example 11] 49.3 g of 6-acetoxy-2,3-benzofuran and 80 g of toluene as a solvent were added to a 2 L flask. This reaction vessel was cooled to −70 ° C. under a nitrogen atmosphere, and deaeration under reduced pressure and nitrogen blowing were repeated 3 times. After the temperature was raised to room temperature, 4.1 g of sulfuric acid was added as a polymerization initiator, the temperature was raised to 60 ° C., and the reaction was carried out for 15 hours. The reaction solution was concentrated to 1/2 and methanol 4.
The white solid obtained was precipitated in a mixed solution of 5 L and 0.5 L of water, filtered, and dried under reduced pressure at 60 ° C. to give a white polymer 42.
g was obtained. This polymer was dissolved again in 0.5 L of methanol and 1.0 L of tetrahydrofuran, 70 g of triethylamine and 15 g of water were added, a deprotection reaction was performed, and the mixture was neutralized with acetic acid. The reaction solution was concentrated and then dissolved in 0.5 L of acetone, and the same precipitation, filtration and drying as described above were performed to obtain 35 g of a white polymer.

The polymer obtained was subjected to ¹³ C, ¹ H-NMR and GPC measurements, and the following analysis results were obtained. Poly-6-hydroxy-2,3-benzofuran weight average molecular weight (Mw) = 8,100 molecular weight distribution (Mw / Mn) = 1.97 This is designated as (polymer 11).

[Synthesis Example 12] Using a 2 L flask,
40 g of the above polymer 11 is added to tetrahydrofuran 400
Dissolve in mL, add 1.4 g of methanesulfonic acid and 12.3 g of ethyl vinyl ether, react at room temperature for 1 hour, add 2.5 g of ammonia water (30%) to stop the reaction, and add this reaction solution to acetic acid water. Crystallize and precipitate using 5 L,
Washing with water twice more and filtering the resulting white solid, 4
After drying under reduced pressure at 0 ° C., 47 g of a white polymer was obtained.

The polymer obtained was subjected to ¹³ C, ¹ H-NMR and GPC measurements, and the following analysis results were obtained. Copolymerization composition ratio 6-hydroxy-2,3-benzofuran: 6-ethoxyethoxy-2,3-benzofuran = 71: 29 Weight average molecular weight (Mw) = 8500 Molecular weight distribution (Mw / Mn) = 1.97 Polymer 12).

[Comparative Synthesis Example 1] Using a 2 L flask, polyhydroxystyrene (Mw = 11,000, M
w / Mn = 1.08) 40 g of tetrahydrofuran 40
Dissolve in 0 mL, add 1.4 g of methanesulfonic acid and 12.3 g of ethyl vinyl ether, react at room temperature for 1 hour,
2.5 g of ammonia water (30%) was added to stop the reaction, and the reaction solution was crystallized and precipitated using 5 L of acetic acid water,
Washing with water twice more and filtering the resulting white solid, 4
After drying under reduced pressure at 0 ° C., 47 g of a white polymer was obtained.

The obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, and the following analysis results were obtained. Copolymerization composition ratio hydroxystyrene: p-ethoxyethoxystyrene =
63.5: 36.5 Weight average molecular weight (Mw) = 13.0
00 Molecular weight distribution (Mw / Mn) = 1.10 This is designated as (Comparative Polymer 1).

[Comparative Synthesis Example 2] To a 2 L flask, 43.0 g of tert-butyl methacrylate and 113.8 g of 4-acetoxystyrene were added, and 130 g of toluene was added as a solvent. This reaction vessel was cooled to −70 ° C. under a nitrogen atmosphere, and deaeration under reduced pressure and nitrogen blowing were repeated 3 times. After warming to room temperature, 4.1 g of AIBN as a polymerization initiator was added,
After raising the temperature to 0 ° C., the reaction was carried out for 15 hours. The reaction solution was concentrated to 1/2, precipitated in a mixed solution of 4.5 L of methanol and 0.5 L of water, and the obtained white solid was filtered and
After drying under reduced pressure at 0 ° C., 125 g of a white polymer was obtained. This polymer was added with 0.5 L of methanol and tetrahydrofuran 1.
Redissolve in 0 L, 70 g of triethylamine, 15 g of water
Was added to carry out a deprotection reaction, and the mixture was neutralized with acetic acid. The reaction solution was concentrated, dissolved in 0.5 L of acetone, and subjected to the same precipitation, filtration and drying as above to obtain 112 g of a white polymer.

The polymer obtained was subjected to ¹³ C, ¹ H-NMR and GPC measurements, and the following analysis results were obtained. Copolymerization composition ratio t-butyl methacrylate: 4-hydroxystyrene = 3
2:68 Weight average molecular weight (Mw) = 12,400 Molecular weight distribution (Mw / Mn) = 1.75 This is designated as (Comparative Polymer 2).

[Examples, Comparative Examples] Evaluation of Exposure Patterning Using the polymers obtained in the above Synthesis Examples and Comparative Synthesis Examples,
A resist material having the composition shown in Table 1 was prepared, and the exposure patterning was evaluated by the following method. The results are shown in Table 1.

The solution having the composition shown in Table 1 was filtered through a 0.2 μm size filter to prepare a resist solution. DUV-30 (manufactured by NISSAN CHEMICAL CO., LTD.) With a film thickness of 55 nm was formed on a silicon wafer, and a resist solution was spin-coated on the substrate.
Bake at 0 ° C for 90 seconds to reduce the resist thickness to 300 nm.
I chose

An excimer laser stepper (Nikon Corporation, NSR-S202A, NA-0.6, σ 0.7)
5, 2/3 ring illumination), and immediately after exposure 1
After baking at 30 ° C. for 90 seconds, development was performed for 60 seconds with an aqueous solution of 2.38% tetramethylammonium hydroxide to obtain a positive pattern.

The obtained resist pattern was evaluated as follows. Evaluation method: 0.20 μm line and space 1:
The exposure amount resolved in 1 was taken as the sensitivity of the resist, and the minimum line width of the line and space separated at this exposure amount was taken as the resolution of the evaluation resist.

[0155]

[Table 1] PGMEA: Propylene glycol monomethyl ether acetate

[0156]

[Chemical 35]

Evaluation of dry etching resistance In the dry etching resistance test, 2 g of the polymer was used as PG.
The polymer solution dissolved in 10 g of MEA and filtered through a filter of 0.2 μm size was spin-coated on a Si substrate to form a film having a thickness of 300 nm, and evaluated under two system conditions. The results are shown in Table 2. (1) Etching test with CHF ₃ / CF ₄ system gas Tokyo Electron Ltd. dry etching equipment TE
The difference in film thickness of the polymer film before and after etching was determined using -8500P. The etching conditions are as shown below. Chamber pressure 40.0Pa RF power 1300W Gap 9mm CHF ₃ gas flow rate 30ml / min CF ₄ gas flow rate 30ml / min Ar gas flow rate 100ml / min time 60sec (2) Etching test with Cl ₂ / BCl ₃ system gas Nidec ANELVA Dry etching system L-50 manufactured by Co., Ltd.
Using 7D-L, the film thickness difference between the polymer film before and after etching was determined. The etching conditions are as shown below. Chamber pressure 40.0 Pa RF power 300 W Gap 9 mm Cl ₂ gas flow rate 30 ml / min BCl ₃ gas flow rate 30 ml / min CHF ₃ gas flow rate 100 ml / min O ₂ gas flow rate 2 ml / min time 60 sec

[0158]

[Table 2]

From the results shown in Tables 1 and 2, the resist material using the polymer compound of the present invention has sufficient resolution and sensitivity and has a small difference in film thickness after etching. It turned out to have.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08F 232/08 C08F 232/08 234/00 234/00 H01L 21/027 H01L 21/30 502R (72) Invention Author Takanobu Takeda 28-1 Nishi-Fukushima, Kubiki-mura, Nakakubiki-gun, Niigata Shin-Etsu Chemical Co., Ltd.Research Center for Advanced Functional Materials Technology (72) Osamu Watanabe 28-1, Nishi-Fukushima, Kubiki-mura, Nakakubiki-gun, Niigata Shin-Etsu Chemical Co., Ltd. Innovator, Advanced Functional Materials Technology Research Co., Ltd. (72) Inventor Koji Hasegawa 28-1, Nishi-Fukushima, Kubiki-mura, Nakakubiki-gun, Niigata Prefecture Shin-Etsu Chemical Co., Ltd. F-term in the Advanced Functional Materials Technology Research Center (reference) 2H025 AA01 AA02 AA04 AA09 AB16 AC04 AC08 AD03 BE00 BE10 BG00 CB08 CB14 CB17 CB45 CC20 FA01 FA12 FA17 4J100 AB02S AB03S AB07S AB08S AB09S AB10S AL08Q AL14Q AL26Q AL39Q AL44Q AM03 Q AM05Q AR09R AR10R AR31P AR32P AR33P AR36P BA02Q BA03P BA03Q BA03R BA03S BA04P BA04R BA04S BA05P BA05R BA05S BA06P BA06R BA06S BA11Q BA15Q BA29Q BA30Q BA75Q BB01P BB01R BB03P BB03R BB05P BB05R BB05S BB07P BB07R BC03Q BC04Q BC07Q BC09Q BC22Q BC23Q BC43Q BC45Q BC53Q BC60Q CA04 CA05 CA06 DA01 JA38

Claims (12)

[Claims] 1. A polymer compound containing a repeating unit represented by the following general formula (1) and a repeating unit having an acid labile group and having a weight average molecular weight of 1,000 to 500,000. Resist material. [Chemical 1] (In the formula, R ¹ is a hydrogen atom, a hydroxy group, or a carbon number of 1 to 4
A linear or branched alkyl group having 1 to 20 carbon atoms
Represents a substitutable alkoxy group or a halogen atom. Further, m is 0 or a positive integer of 1 to 4. X represents an oxygen atom, a sulfur atom, or a -NR- group, R represents a hydrogen atom,
It is a linear or branched alkyl group having 1 to 4 carbon atoms, or a hydroxy group. p is a positive number. ) 2. A polymer compound containing a repeating unit represented by the following general formula (2) and a repeating unit having an acid labile group and having a weight average molecular weight of 1,000 to 500,000. Resist material. [Chemical 2] (In the formula, R ¹ and R ² are the same or different hydrogen atoms, a hydroxy group, a linear or branched alkyl group having 1 to 4 carbon atoms, a substituted alkoxy group having 1 to 20 carbon atoms, or a halogen atom. In addition, m and n are 0 or a positive integer of 1 to 4. X represents an oxygen atom, a sulfur atom, or a -NR- group, R is a hydrogen atom, a straight chain having 1 to 4 carbon atoms. A branched or branched alkyl group or a hydroxy group, p and q are positive numbers.) 3. A repeating unit represented by the following general formula (3):
A polymer compound having a position
Gist material. [Chemical 3] (In the formula, R¹, X, m, p are R as described above.³Is a hydrogen atom
Or represents a methyl group, R ^FourIs a hydrogen atom, methyl group,
Represents a coxycarbonyl group, a cyano group, or a halogen atom.
And R^FiveRepresents an acid labile group. R is a positive number
It ) 4. A resist material containing a polymer compound having a repeating unit represented by the following general formula (4). [Chemical 4] (In the formula, R ¹ , R ³ , R ⁴ , R ⁵ , and X are as described above, R ⁶ is a hydrogen atom or a methyl group, m, p, and r are as described above, and o is 0 or 1 to 1. (4 is a positive integer, and s is a positive number.) 5. A resist material containing a polymer compound having a repeating unit represented by the following general formula (5). [Chemical 5] (In the formula, R ¹ , R ² , and X are as described above, R ³ represents a hydrogen atom or a methyl group, R ⁴ represents a hydrogen atom, a methyl group, an alkoxycarbonyl group, a cyano group, or a halogen atom; ⁵ represents an acid labile group, and m and n are 0 or 1.
Is a positive integer of ˜4. Further, p and q are positive numbers, and r is a positive number. ) 6. A resist material containing a polymer compound having a repeating unit represented by the following general formula (6). [Chemical 6] (In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and X are as described above.
R ⁶ represents a hydrogen atom or a methyl group, m, n, q and p are as described above, o is 0 or a positive integer of 1 to 4, and s
Is a positive number. ) 7. The resist material according to claim 1, wherein the repeating unit p has the following general formula (1):
A resist material which is represented by a). [Chemical 7] (In the formula, R ⁵ and X are as described above, p is a positive number, and m is 0 or a positive integer of 1 to 4.) 8. The resist material according to claim 2, 5 or 6, wherein the repeating unit q is represented by the following general formula (2a). [Chemical 8] (In the formulas, R ² and R ⁵ are as described above, q is a positive number, and m is 0 or a positive integer of 1 to 4.) 9. The polymer compound according to claim 1 as an organic solvent (A) and a base resin (B),
(C) A chemically amplified positive resist composition containing an acid generator. 10. An organic solvent (A), a polymer compound according to any one of claims 1 to 8 as a base resin (B), an acid generator (C) and a dissolution inhibitor (D). And a chemically amplified positive resist material. 11. The chemically amplified positive resist composition according to claim 9 or 10, further comprising a basic compound as an additive (E). 12. A step of applying the resist material according to claim 1 onto a substrate, a step of exposing with a high energy beam or an electron beam through a photomask after heat treatment, which is required. And then developing with a developing solution.