JPH10310642A - Novel high-molecular silicone compound, chemically amplified positive resist material, and pattern formation method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a high-molecular silicone compd. that is suitable for a base resin of a resist useful for fine processing with an electron beam or ultraviolet rays since it has phenolic hydroxyl groups a part of which have hydrogen atoms replaced by acid-unstable groups and a part of the rest of which have been crosslinked intramolecularly and/or intermolecularly by crosslinking groups having C-O-C groups. SOLUTION: This silicone compd. has repeating units of the formula (wherein Me is methyl; x is 1-5; 0.001<=y<=0.05; and z is 1-3) and a wt. average mol.wt. of 5,000-50,000. In the compd., a part of phenolic hydroxyl groups have hydrogen atoms replaced by acid-unstable groups and a part of the rest of the hydroxyl groups are crosslinked intramolecularly and/or intermolecularly by crosslinking groups having C-O-C groups and formed by the reaction of an alkenyl ether compd. with a halogenated alkyl ether compd. The sum of amts. of the acid- unstable group and the crosslinking group is higher than 0 mol.% and not higher than 80 mol.% of the amt. of phenolic hydroxyl group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polymer silicone compound having one or more acid labile groups, which is further cross-linked by a cross-linking group having a C--O--C group within and / or between molecules. A novel polymer silicone compound useful as a base resin for a chemically amplified positive resist material, and containing this polymer silicone compound as a base resin, which can be used for high ultraviolet rays, electron beams, X-rays and the like. The present invention relates to a chemically amplified positive resist material and a pattern forming method which have high sensitivity to energy rays and can form a resist pattern by developing with an alkaline aqueous solution and which is suitable for fine processing technology.

[0002]

2. Description of the Related Art In recent years,
As the integration and speed of LSIs increase, the pattern rule is required to be finer. With the light exposure currently used as a general-purpose technology, the essential resolution limit derived from the wavelength of the light source is approaching. It is getting. In light exposure using a g-line (436 nm) or an i-line (365 nm) as a light source, a pattern rule of about 0.5 μm is limited, and the integration degree of an LSI manufactured using this is 16 Mbit D
Up to RAM equivalent. However, LSI prototypes have already been made at this stage, and there is an urgent need to develop further miniaturization techniques.

[0003] For this reason, Ito et al. Proposed PBOCST in which the hydroxyl group of polyhydroxystyrene was protected with a tert-butoxycarbonyloxy group (t-Boc group).
Since the proposal of a chemically amplified positive resist material in which an acid generator of an onium salt is added to such a resin, various high-sensitivity and high-resolution resist materials have been developed. However, although all of these chemically amplified positive resist materials have high sensitivity and high resolution, forming a fine pattern with a high aspect ratio is difficult in view of the mechanical strength of the pattern obtained from them. It was difficult.

[0004] Further, the above polyhydroxystyrene is used as a base resin,
Many chemically amplified positive resist materials having sensitivity to radiation have been proposed. However, in order to form a pattern having a high aspect ratio on a stepped substrate, a two-layer resist method is excellent, whereas all of the above resist materials are based on a single-layer resist method, and the problem of a substrate step difference still exists. At present, there is a problem of light reflection from the substrate and a problem of difficulty in forming a pattern having a high aspect ratio.

On the other hand, conventionally, it has been known that a two-layer resist method is excellent for forming a pattern having a high aspect ratio on a stepped substrate. It is known that a silicone polymer having a hydrophilic group such as a hydroxy group or a carboxyl group is required for developing with a liquid. However, in the case of silanol in which a hydroxyl group is directly bonded to silicone, a cross-linking reaction occurs due to an acid, so that application to a chemically amplified positive resist material has been difficult.

In recent years, as a silicone-based chemically amplified positive resist material which solves these problems, a part of the phenolic hydroxyl group of polyhydroxybenzylsilsesquioxane, which is a stable alkali-soluble silicone polymer, is t-substituted.
Using the one protected with -Boc group as the base resin,
A chemically amplified silicone-based positive resist material combining this with an acid generator has been proposed (Japanese Patent Laid-Open No. 6-1 / 1994).
No. 18651, SPIE vol. 1952 (199
3) 377 etc.).

However, some of the hydroxy groups of these polyhydroxybenzylsilsesquioxanes are replaced with tB
A resist material based on a silicone polymer protected by an oc group has a problem that a tailing phenomenon occurs at an interface with a lower layer film, and a surface insoluble layer is easily formed on an upper silicone resist film. . The tailing and the poorly soluble surface layer are not suitable for fine processing because the dimensional accuracy of the pattern of the resist film cannot be controlled.

The present invention has been made in view of the above circumstances, and has only high sensitivity and high resolution, and can be suitably used as a material for a two-layer resist method particularly suitable for forming a pattern having a high aspect ratio. Novel polymeric silicone compound useful as a base polymer of a chemically amplified positive resist material capable of forming a pattern having excellent heat resistance, a chemically amplified positive resist material containing the compound as a base polymer, and pattern formation The aim is to provide a method.

[0009]

Means for Solving the Problems and Embodiments of the Invention The present inventors have conducted intensive studies to achieve the above object, and as a result, have a phenolic hydroxyl group. Part is substituted with at least one kind of acid labile group, and a part of the remaining phenolic hydroxyl groups is further cross-linked with a cross-linking group having an intramolecular and / or intermolecular C—O—C group. Having a repeating unit represented by the following general formula (1), preferably the general formula (2), more preferably the general formula (3), A high-molecular-weight silicone compound having an acid labile group and the above-mentioned crosslinking group is used as a base resin, and an acid generator is added thereto. The combined chemically amplified positive resist material and the chemically amplified positive resist material further mixed with a basic compound enhances the resist dissolution contrast, and especially exhibits the effect of increasing the dissolution rate after exposure, resulting in high resolution. It has been found that it is excellent in exposure latitude and process adaptability, has high practicality, and is very effective as a resist material for VLSI which is advantageous for precise fine processing.

[0010] Further, the use of a polymer silicone compound crosslinked intramolecularly and / or intermolecularly, in particular, intermolecularly, as the base resin increases the molecular weight and the softening point, thereby improving heat resistance. It has been found that it is suitable for the layer resist method.

That is, the present invention provides the following novel high molecular silicone compound, a chemically amplified positive resist material containing the same, and a pattern forming method.

Claim 1: A phenolic hydroxyl group has at least one hydrogen atom in the phenolic hydroxyl group.
Weight average of a high molecular weight silicone compound substituted with a kind of acid labile group, which is further crosslinked with a crosslinkable group having a C—O—C group in a part of the remaining phenolic hydroxyl groups. A high molecular weight silicone compound having a molecular weight of 5,000 to 50,000.

In a preferred embodiment, the phenolic hydroxyl group of the high molecular silicone compound having a repeating unit represented by the following general formula (1) is partially substituted with an acid labile group, and the remaining phenolic hydroxyl group is partially substituted. Are cross-linked by a cross-linking group having a C—O—C group in a molecule and / or between molecules obtained by reacting a part of the compound with an alkenyl ether compound or a halogenated alkyl ether compound. The total amount of the phenolic hydroxyl groups is more than 0 mol% and more than 80 mol%
The polymer silicone compound according to claim 1, wherein the ratio is as follows.

[0014]

Embedded image (In the formula, Me represents a methyl group, x is an integer of 1 to 5, y is a positive number satisfying 0.001 ≦ y ≦ 0.05, z
Is an integer of 1 to 3. )

In a preferred embodiment, the phenolic hydroxyl group represented by R of the high molecular silicone compound having a repeating unit represented by the following general formula (2) is reacted with an alkenyl ether compound or a halogenated alkyl ether compound. The polymer silicone compound according to claim 2, wherein the polymer silicone compound is cross-linked by a cross-linking group having a C-O-C group between molecules.

[0016]

Embedded image (Wherein Me is a methyl group, R is a hydroxyl group or an OR ¹ group, at least one is a hydroxyl group. R ¹ is an acid labile group, m is 0 or an integer of 1 to 5, n Is an integer of 1 to 5, and is a number satisfying m + n ≦ 5, and x is 1 to 5.
5, y is a positive number satisfying 0.001 ≦ y ≦ 0.05, and z is an integer of 1 to 3. p and q are positive numbers and satisfy p + q = 1. )

In a preferred embodiment, the hydrogen atom of the phenolic hydroxyl group represented by R in the high molecular silicone compound having a repeating unit represented by the following general formula (3) is removed, and the oxygen atom is converted into the following general formula (4a) or (4a). CO represented by 4b)
The polymer silicone compound according to claim 3, which is crosslinked intra- and / or intermolecularly by a cross-linking group having a -C group.

[0018]

Embedded image (Wherein Me is a methyl group, R is a hydroxyl group or an OR ¹ group, at least one is a hydroxyl group, R ¹ is an acid labile group, R ² and R ³ are a hydrogen atom or a carbon atom 1-8 linear, branched or cyclic alkyl group, R ⁴ represents a may monovalent which may have a hetero atom of a hydrocarbon group having 1 to 18 carbon atoms, R ² and R ³ , R ² and R ⁴ , and R ³ and R ⁴ may form a ring, and when forming a ring, R ² , R ³ , R
⁴ represents a linear or branched alkylene group having 1 to 18 carbon atoms. R ⁵ is a tertiary alkyl group, each alkyl moiety has trialkylsilyl group having 1 to 6 carbon atoms having 4 to 20 carbon atoms, or oxoalkyl groups of 4 to 20 carbon atoms -
And a group represented by CR ² R ³ OR ⁴ . p1 and p2 are positive numbers, q1 and q2 are 0 or positive numbers, and 0 <p1 / (p1
+ P2 + q1 + q2) ≦ 0.8, 0 ≦ q1 / (p1 + p
2 + q1 + q2) ≦ 0.8, 0 ≦ q2 / (p1 + p2 +
q1 + q2) ≦ 0.8, which satisfies p1 + p2 + q1 + q2 = 1, but q1 and q2 do not become 0 at the same time. a is 0 or an integer of 1 to 6. m, n, x,
y and z each have the same meaning as described above. )

[0019]

Embedded image (Wherein, R ⁶ and R ⁷ represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms. Alternatively, R ⁶ and R ⁷ may form a ring, When a ring is formed, R ⁶ and R ^{7 each} represent a linear or branched alkylene group having 1 to ⁸ carbon atoms, and R ⁸ represents a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms. And d is 0 or an integer of 1 to 10. A represents a c-valent aliphatic or alicyclic saturated hydrocarbon group having 1 to 50 carbon atoms, an aromatic hydrocarbon group or a heterocyclic group, May have a heteroatom interposed,
Some of the hydrogen atoms bonded to the carbon atoms are hydroxyl groups,
It may be substituted by a carboxyl group, an acyl group or a fluorine atom. B is -CO-O-, -NHCO-O
-Or -NHCONH-. c is 2 to 8, c 'is 1
-7. )

Claim 5: The crosslinking group having a C—O—C group represented by the general formula (4a) or (4b) is represented by the following general formula (4a ′) or (4b ′) Chemically amplified positive resist material.

[0021]

Embedded image (Wherein, R ⁶ and R ⁷ represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms. Alternatively, R ⁶ and R ⁷ may form a ring, When a ring is formed, R ⁶ and R ^{7 each} represent a linear or branched alkylene group having 1 to ⁸ carbon atoms, and R ⁸ represents a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms. And d is an integer of 0 or 1 to 5. A ′ is a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms, an alkyltriyl group or an alkyltetrayl group having a c ″ valency. Or an arylene group having 6 to 30 carbon atoms, and these groups may have a hetero atom interposed;
Some of the hydrogen atoms bonded to the carbon atoms are hydroxyl groups,
It may be substituted by a carboxyl group, an acyl group or a fluorine atom. B is -CO-O-, -NHCO-O
-Or -NHCONH-. c '' is 2 to 4,
c ″ ′ is an integer of 1 to 3. )

Claim 6: (A): an organic solvent (B): any one of claims 1 to 5 as a base resin
4. A chemically amplified positive resist material comprising the polymer silicone compound (C): an acid generator according to the above item (1).

(7) The chemically amplified positive resist material according to (6), further comprising (D) a dissolution controlling agent.

In a preferred embodiment, the composition further comprises (E) a basic compound as an additive.
The positive resist composition according to any one of the preceding claims.

Claim 9: Further, as a base resin different from the components (F) and (B), a hydrogen atom of a phenolic hydroxyl group of a high molecular silicone compound having a repeating unit represented by the following general formula (1) is used. A weight average molecular weight of 3,000 to 300, partially substituted by one or two or more acid labile groups in a proportion of 0 to 80 mol% on average as a whole.
9. The chemically amplified positive resist material according to claim 6, wherein 000 high molecular silicone compounds are blended.

[0026]

Embedded image (In the formula, Me represents a methyl group, x is an integer of 1 to 5, y is a positive number satisfying 0.001 ≦ y ≦ 0.05, z
Is an integer of 1 to 3. )

Claim 10: (i) a step of applying the chemically amplified positive resist material according to any one of claims 6 to 9 onto a substrate;
i) Next, after the heat treatment, a wavelength of 30
A pattern forming method, comprising: a step of exposing to a high-energy ray or an electron beam of 0 nm or less; and (iii) a step of performing a heat treatment as necessary and then developing with a developer.

Here, the high molecular silicone compound is
The intramolecular and / or intermolecular C-O-C obtained by the reaction of a part of the phenolic hydroxyl group with an alkenyl ether compound or a halogenated alkyl ether compound.
It is cross-linked by a cross-linking group having a group. When such a high molecular silicone compound is blended in a resist material as a base resin, in particular, since it is crosslinked by a crosslinking group having a C—O—C group, the dissolution inhibiting property is large and the dissolution contrast after exposure is large. Has advantages.

That is, generally, in order for polysiloxane to be used as a positive resist material, a polysiloxane skeleton having an alkali-soluble property and an alkali-soluble functional group protected by an acid-labile protecting group must be used. Become. As the alkali-soluble polysiloxane that is stably supplied, for example, a poly (p-) comprising a unit represented by the following formula (1):
Hydroxybenzylsilsesquioxane).

[0030]

Embedded image

On the other hand, an alkali-soluble functional group, that is, an acid-labile protecting group for protecting a hydroxyl group in this case, includes a t-Boc group (tert-butoxycarbonyl group). From the viewpoint, a polysiloxane compound used in a positive resist material is represented by the following formula (5) (JP-A-6-118).
No. 651).

[0032]

Embedded image (In the formula, t-Bu represents a tert-butyl group.)

Here, t-Bo used as a protecting group was used.
The c group is eliminated by the action of an acid generated from the acid generator upon irradiation with energy rays, and the polysiloxane becomes alkali-soluble and can be developed.

In such a situation, the present inventors:
In order to solve the problem of the tailing generated at the interface between the silicone-based resist material used in the two-layer resist method and the lower layer and the problem of the hardly soluble layer appearing on the surface, the above-mentioned t
In the elimination reaction of the -Boc group in the resist film, it was confirmed from the analysis by FT-IR and the like that the following side reaction had occurred. It was found that it was due to expression.

[0035]

Embedded image

That is, the tert-butyl cation generated by the elimination of the t-Boc group with an acid reacts with the phenolic hydroxyl group again, so that the phenolic hydroxyl group is again protected and the desired alkali solubility is inhibited. For this reason, it was confirmed that the bottom layer was skirted at the interface with the lower layer, and a poorly soluble layer was developed on the film surface.

The t-Boc group is one of various hydroxyl-protecting groups that has an extremely high activation energy for elimination by an acid and is difficult to be eliminated. Therefore, t-
Removal of the Boc group requires a strong acid such as trifluoromethanesulfonic acid. When a weak acid other than trifluoromethanesulfonic acid is used, the progress of the elimination reaction cannot be promoted, and the sensitivity of the resist deteriorates.

In the resist film, trifluoromethanesulfonic acid generated due to the deprotection of the t-Boc group diffuses into the lower layer film or is deactivated due to contamination from the lower layer film. At the interface, the acid concentration decreases, so the deprotection reaction does not proceed sufficiently,
A portion that does not become alkali-soluble occurs, and a tailing occurs. On the other hand, on the resist film surface, trifluoromethanesulfonic acid evaporates or is deactivated due to contamination from the atmosphere, so that the acid concentration decreases also on the resist film surface, and thus the deprotection group reaction sufficiently proceeds. However, a portion that does not become alkali-soluble is formed, and a surface hardly soluble layer is developed.

Means for solving the above-mentioned problems of tailing and the formation of a poorly soluble surface layer include introduction of an acetal group into a phenolic hydroxyl group. When the acetal group alone is added to the polymer, the above-mentioned re-reaction of the leaving group does not occur, and the elimination reaction proceeds sensitively with a weak acid, so that a hardly soluble surface layer or tailing occurs. Absent.

However, there is a disadvantage that the pattern shape becomes extremely thin with the lapse of time from exposure to heat treatment due to the sensitive reaction with a weak acid. In addition, since the dissolution inhibiting effect on alkali is low, a highly substituted product must be used in order to obtain a dissolution contrast, and therefore, there is a disadvantage that heat resistance is poor.

As described above, such a polymer has an intramolecular and / or a crosslinkable group having a C—O—C group obtained by the reaction of a phenolic hydroxyl group with an alkenyl ether compound and / or a halogenated alkyl ether compound. Alternatively, a resist material using a high molecular silicone compound cross-linked between molecules exhibits dissolution inhibition with a small amount of cross-linking, and improves heat resistance due to an increase in molecular weight due to cross-linking. In addition, since the cross-linking group is eliminated after exposure rather than before exposure, the dissolution contrast of the resist film can be increased by reducing the molecular weight of the polymer, resulting in high sensitivity and high resolution. . In addition, since there are few problems with the surface hardly soluble layer and the occurrence of tailing, it is possible to arbitrarily control the pattern dimension and the pattern shape by the composition, and it is a chemically amplified positive type with excellent process adaptability. Knowing that it will be a resist material,
The present invention has been accomplished.

Now, the present invention will be described in more detail. The novel high molecular silicone compound of the present invention has a phenolic hydroxyl group, and a part of hydrogen atoms of the phenolic hydroxyl group is at least one kind of acid labile group. Is further cross-linked with a cross-linking group having a C—O—C group in a part of the remaining phenolic hydroxyl group and a C—O—C group.
0 to 50,000.

As the high molecular silicone compound, a part of hydrogen atoms of a phenolic hydroxyl group of the high molecular silicone compound having a repeating unit represented by the following general formula (1) is partially substituted by an acid labile group, and Is cross-linked by a cross-linking group having a C—O—C group within and / or between molecules obtained by reacting a part of the phenolic hydroxyl group with an alkenyl ether compound or a halogenated alkyl ether compound. A high molecular silicone compound substituted with a total amount of the stable group and the cross-linking group of more than 0 mol% and not more than 80 mol% of the average of all hydrogen atoms of the phenolic hydroxyl group can be obtained.

[0044]

Embedded image (In the formula, Me represents a methyl group, x is an integer of 1 to 5, y is a positive number satisfying 0.001 ≦ y ≦ 0.05, z
Is an integer of 1 to 3. )

Specific examples of such a high molecular silicone compound include a phenolic hydroxyl group represented by R and an alkenyl ether compound or a halogenated alkyl ether of a high molecular silicone compound having a repeating unit represented by the following general formula (2). It is cross-linked by a cross-linking group having a C—O—C group in the molecule and / or between the molecules obtained by the reaction with the compound, and the total amount of the acid labile group and the cross-linking group is phenolic in the formula (1). It can be a high molecular weight silicone compound having a ratio of more than 0 mol% and not more than 80 mol% of the average of all hydroxyl groups.

[0046]

Embedded image (Wherein Me is a methyl group, R is a hydroxyl group or an OR ¹ group, at least one is a hydroxyl group. R ¹ is an acid labile group, m is 0 or an integer of 1 to 5, n Is an integer of 1 to 5, and is a number satisfying m + n ≦ 5, and x is 1 to 5.
5, y is a positive number satisfying 0.001 ≦ y ≦ 0.05, and z is an integer of 1 to 3. p and q are positive numbers and satisfy p + q = 1. )

The acid labile group substituted with the hydrogen atom of the phenolic hydroxyl group or the acid labile group of R ¹ includes:
Although various selections are made, in particular, a group represented by the following general formula (6), a group represented by the following general formula (7), a tertiary alkyl group having 4 to 20 carbon atoms, and each alkyl group having 1 to 6 carbon atoms
And an oxoalkyl group having 4 to 20 carbon atoms.

[0048]

Embedded image (R ² and R ³ are each a hydrogen atom or a group having 1 to 8 carbon atoms, preferably 1
Represents a linear, branched or cyclic alkyl group having 1 to ⁵ carbon atoms, more preferably 1 to ⁵ carbon atoms, preferably 1 to 12, more preferably 1 to 12, more preferably 1 to 8 carbon atoms. A monovalent hydrocarbon group which may have a hetero atom, wherein R ² and R ³ , R ² and R ⁴ , and R ³ and R ⁴ may form a ring; Is R ² , R ³ and R ⁴ each have 1 carbon atom
To 18, preferably 1 to 10, more preferably 1 to 8, linear or branched alkylene groups. R ⁵ has 4 to 20 carbon atoms, preferably 4 to 15, more preferably 4 to 1 carbon atoms.
0 tertiary alkyl group, each alkyl group has 1 carbon atom
And oxoalkyl groups having 4 to 20 carbon atoms, preferably 4 to 15 carbon atoms, more preferably 4 to 10 carbon atoms, or groups represented by the above general formula (6). a is 0
Or a positive integer of 1 to 6. )

R ² and R ³ have 1 to 8 carbon atoms, preferably 1 to
5, more preferably 1 to 3, linear, branched or cyclic alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, t
Examples thereof include an tert-butyl group, a cyclohexyl group, and a cyclopentyl group.

R ⁴ represents a linear, branched or cyclic alkyl group, phenyl group, p-methylphenyl group, p-
An unsubstituted or substituted aryl group such as an alkoxy-substituted phenyl group such as an ethylphenyl group or a p-methoxyphenyl group, an aralkyl group such as a benzyl group or a phenethyl group, or an oxygen atom interposed in these groups or bonded to a carbon atom Examples of such groups include an alkyl group represented by the following formula, in which a hydrogen atom is substituted by a hydroxyl group, or two hydrogen atoms are substituted by an oxygen atom to form a carbonyl group.

[0051]

Embedded image

Examples of the tertiary alkyl group having 4 to 20 carbon atoms for R ⁵ include a tert-butyl group, a 1-methylcyclohexyl group, a 2- (2-methyl) adamantyl group and a te-butyl group.
An rt-amyl group and the like can be mentioned.

Each alkyl group of R ⁵ has 1 to 1 carbon atoms.
Examples of the trialkylsilyl group 6 include a trimethylsilyl group, a triethylsilyl group, and a dimethyl-tert-butylsilyl group. The oxoalkyl group of 4 to 20 carbon atoms R ^5, 3- oxoalkyl group, or a group, and the like represented by the following formula.

[0054]

Embedded image

As the acid labile group represented by the above formula (6), specifically, for example, 1-methoxyethyl group, 1-ethoxyethyl group, 1-n-propoxyethyl group, 1-isopropoxyethyl group, 1-n-butoxyethyl group, 1
-Isobutoxyethyl group, 1-sec-butoxyethyl group, 1-tert-butoxyethyl group, 1-tert-
An amyloxyethyl group, a 1-ethoxy-n-propyl group,
Linear or branched acetal groups such as 1-cyclohexyloxyethyl group, 1-methoxypropyl group, 1-ethoxypropyl group, 1-methoxy-1-methyl-ethyl group, 1-ethoxy-1-methyl-ethyl group And a cyclic acetal group such as a 2-tetrahydrofuranyl group and a 2-tetrahydropyranyl group, and preferably a 1-ethoxyethyl group, a 1-n-butoxyethyl group and a 1-ethoxypropyl group. On the other hand, examples of the acid labile group of the above formula (7) include a tert-butoxycarbonyl group,
tert-butoxycarbonylmethyl group, tert-amyloxycarbonyl group, tert-amyloxycarbonylmethyl group, 1-ethoxyethoxycarbonylmethyl group,
2-tetrahydropyranyloxycarbonylmethyl group,
And a 2-tetrahydrofuranyloxycarbonylmethyl group. Further, the acid labile group has 4 to 2 carbon atoms.
0 tertiary alkyl group, each alkyl group has 1 carbon atom
And an oxoalkyl group having 4 to 20 carbon atoms represented by the following formula.

[0056]

Embedded image

[0057]

Embedded image

Further, examples of the crosslinking group having a C—O—C group include groups represented by the following general formula (4a) or (4b).

[0059]

Embedded image (Wherein, R ⁶ and R ⁷ represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms. Alternatively, R ⁶ and R ⁷ may form a ring, When a ring is formed, R ⁶ and R ^{7 each} represent a linear or branched alkylene group having 1 to ⁸ carbon atoms, and R ⁸ represents a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms. And d is 0 or an integer of 1 to 10. A represents a c-valent aliphatic or alicyclic saturated hydrocarbon group having 1 to 50 carbon atoms, an aromatic hydrocarbon group or a heterocyclic group, May have a heteroatom interposed,
Some of the hydrogen atoms bonded to the carbon atoms are hydroxyl groups,
It may be substituted by a carboxyl group, an acyl group or a fluorine atom. B is -CO-O-, -NHCO-O
-Or -NHCONH-. c is 2 to 8, c 'is 1
-7. )

Here, as the linear, branched or cyclic alkyl group having 1 to 8 carbon atoms for R ⁶ and R ⁷ , the same as those described above can be exemplified. R ⁸ carbon number 1
Examples of the linear, branched or cyclic alkylene group of 10 to 10 include a methylene group, an ethylene group, a propylene group, an isopropylene group, an n-butylene group, an isobutylene group, a cyclohexylene group and a cyclopentylene group. be able to. A specific example of A will be described later. This crosslinking group (4
a) and (4b) are derived from alkenyl ether compounds and halogenated alkyl ether compounds described below.

As is apparent from the value of c ′ in the above formulas (4a) and (4b), the crosslinking group is not limited to divalent but trivalent to trivalent.
It may be an octavalent group. For example, divalent crosslinking groups are represented by the following formulas (4a ″) and (4b ″), and trivalent crosslinking groups are represented by the following formulas (4a ′ ″) and (4b ′ ″) Things.

[0062]

Embedded image Preferred crosslinking groups are those represented by the following general formula (4a ′) or (4a ′).
b ′).

[0063]

Embedded image (Wherein, R ⁶ and R ⁷ represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms. Alternatively, R ⁶ and R ⁷ may form a ring, When a ring is formed, R ⁶ and R ^{7 each} represent a linear or branched alkylene group having 1 to ⁸ carbon atoms, and R ⁸ represents a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms. And d is an integer of 0 or 1 to 5. A ′ is a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms, an alkyltriyl group or an alkyltetrayl group having a c ″ valency. Or an arylene group having 6 to 30 carbon atoms, and these groups may have a hetero atom interposed;
Some of the hydrogen atoms bonded to the carbon atoms are hydroxyl groups,
It may be substituted by a carboxyl group, an acyl group or a fluorine atom. B is -CO-O-, -NHCO-O
-Or -NHCONH-. c '' is 2 to 4,
c ″ ′ is an integer of 1 to 3. )

As a specific example of the high molecular silicone compound of the present invention, a hydrogen atom of a phenolic hydroxyl group represented by R of a high molecular silicone compound having a repeating unit represented by the following general formula (3) can be obtained. The terminal oxygen atom is a C represented by the above general formula (4a) or (4b)
It is cross-linked intramolecularly and / or intermolecularly by a divalent or higher valent cross-linking group having a -OC group, and the total amount of the acid labile group and the cross-linking group is the average of all phenolic hydroxyl groups in the formula (1). High molecular silicone compounds having a ratio of more than 0 mol% and 80 mol% or less can be mentioned.

[0065]

Embedded image (Wherein Me is a methyl group, R is a hydroxyl group or an OR ¹ group, at least one is a hydroxyl group, R ¹ is an acid labile group, R ² and R ³ are a hydrogen atom or a carbon atom 1-8 linear, branched or cyclic alkyl group, R ⁴ represents a may monovalent which may have a hetero atom of a hydrocarbon group having 1 to 18 carbon atoms, R ² and R ³ , R ² and R ⁴ , and R ³ and R ⁴ may form a ring, and when forming a ring, R ² , R ³ , R
⁴ represents a linear or branched alkylene group having 1 to 18 carbon atoms. R ⁵ is a tertiary alkyl group, each alkyl moiety has trialkylsilyl group having 1 to 6 carbon atoms having 4 to 20 carbon atoms, or oxoalkyl groups of 4 to 20 carbon atoms -
And a group represented by CR ² R ³ OR ⁴ . p1 and p2 are positive numbers, q1 and q2 are 0 or positive numbers, and 0 <p1 / (p1
+ P2 + q1 + q2) ≦ 0.8, 0 ≦ q1 / (p1 + p
2 + q1 + q2) ≦ 0.8, 0 ≦ q2 / (p1 + p2 +
q1 + q2) ≦ 0.8, which satisfies p1 + p2 + q1 + q2 = 1, but q1 and q2 do not become 0 at the same time. a is 0 or an integer of 1 to 6. m, n, x,
y and z each have the same meaning as described above. )

In the general formula (3), p1 and p2 are positive numbers, q1 and q2 are 0 or positive numbers, and p1 + p2 =
p, q1 + q2 = q. In this case, p1 is 0 <p
1 / (p1 + p2 + q1 + q2) ≦ 0.8, preferably 0.02 <p1 / (p1 + p2 + q1 + q2) ≦
0.4 should be satisfied. If p1 is too small, the effect of the crosslinking group is not exhibited, and if p1 is too large, gelation may occur in the production of the high molecular silicone compound. Also, q1 and q2 are 0 ≦ q1 / (p1 + p2 + q1 + q
2) ≦ 0.8, 0 ≦ q2 / (p1 + p2 + q1 + q2)
≦ 0.8, which satisfies p1 + p2 + q1 + q2 = 1, and q1 and q2 never become 0 at the same time. More preferably, 0 ≦ q1 / (p1 + p2 + q1 + q2) ≦ 0.
5, 0 ≦ q2 / (p1 + p2 + q1 + q2) ≦ 0.3 is good. At this time, if the ratio of q1 and q2 is large, the solubility in alkali is lost, the film thickness is changed during alkali development, the stress in the film or the generation of bubbles is generated, and the number of hydrophilic groups is reduced. In some cases, the adhesion to the lower layer film is poor. The sum of q1 and q2 is 0 <(q1 + q
2) / (p1 + p2 + q1 + q2) ≦ 0.3, especially 0.
05 ≦ (q1 + q2) / (p1 + p2 + q1 + q2) ≦
It is preferably 0.3. Further, by appropriately selecting the values of p1, q1 and q2 within the above range, the pattern size control and the pattern shape control can be arbitrarily performed.

In the high molecular silicone compound of the present invention, the content of the above-mentioned crosslinkable group having a C—O—C group and the acid labile group affects the dissolution rate contrast of the resist film, and controls the dimension of the pattern and the pattern. This is related to the characteristics of the resist material such as shape control of the resist.

Here, the general formulas (1), (2),
Explaining y in (3), y is 0.00
It is a positive number satisfying 1 ≦ y ≦ 0.05.
Me ₃ ) _y blocks the terminal silanol of the polysiloxane represented by the general formulas (1), (2) and (3). If the terminal silanol is not blocked, the resist material is not preferred because it exerts stability such as an increase in particles during storage and deterioration in sensitivity.

Examples of the high molecular silicone compound include those represented by the following formulas (3′-1) and (3′-2).

[0070]

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[0071]

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The formula (3′-1) shows an intermolecular bond, and the formula (3′-2) shows an intramolecular bond, and these may be used alone or in combination.

R ^{2 to} R ⁵ , p1, p2, q1, q2, m,
n, x, y, and z have the same meanings as above.

Wherein Q is a crosslinking group having a C—O—C group,
Typically, the crosslinking group represented by the above formula (4a) or (4b), particularly the formula (4a ″), (4b ″) or the formula (4)
a '''),(4b'''), most preferably the formula (4
a ′) and (4b ′). In this case, when the crosslinking group is trivalent or more, in the above formula (3),
Q is bonded to three or more of the following units.

[0075]

Embedded image (In the formula, R, x, y, and z each have the same meaning as described above.)

In the polymer silicone compound of the present invention, the hydrogen atom of the phenolic hydroxyl group is partially substituted with an acid labile group and the above-mentioned C—O—C group crosslinking group. , More preferably, a polymer silicone of the formula (1)
The total of the acid labile groups and the cross-linking groups exceeds an average of 0 mol% with respect to all the hydrogen atoms of the phenolic hydroxyl groups of the phenolic compound.
It is preferably at most mol%, particularly preferably 2 to 50 mol%.

In this case, the proportion of the crosslinking group having a C—O—C group is more than 0 mol% on average and not more than 80 mol%, especially 0.2 mol%.
~ 20 mol% is preferred. When the content is 0 mol%, the contrast of the alkali dissolution rate becomes small, and the advantage of the cross-linking group cannot be brought out, resulting in poor resolution. On the other hand, if it exceeds 80 mol%, it crosslinks too much and gels, loses its solubility in alkali, causes a change in film thickness, the generation of stress in the film or the generation of bubbles during alkali development, and the reduction of hydrophilic groups. Therefore, the adhesion to the substrate may be poor.

The ratio of acid labile groups is 0 mol% on average.
Is more than 80 mol%, especially 10 to 50 mol%. At 0 mol%, the contrast of the alkali dissolution rate becomes small, and the resolution becomes poor. On the other hand, if it exceeds 80 mol%, the solubility in alkali may be lost, or the affinity with a developing solution may be reduced during alkali development, resulting in poor resolution.

The dimensions of the pattern and the shape of the pattern can be controlled arbitrarily by appropriately selecting the values of the crosslinking group having a C—O—C group and the acid labile group within the above ranges. In the polymer silicone compound of the present invention, the content of the crosslinking group having a C—O—C group and the content of an acid labile group affect the contrast of the dissolution rate of the resist film, and control the pattern dimension, the pattern shape and the like. It is related to the characteristics of the resist material.

The polymer silicone compound of the present invention has a weight average molecular weight of 5,000 to 50,000, preferably 5,000 to 10,000. If the weight average molecular weight is less than 5,000, the desired plasma etching resistance may not be obtained or the effect of inhibiting dissolution in an alkaline aqueous solution may be reduced. If it exceeds 50,000, it may be difficult to dissolve in a general-purpose resist solvent. is there.

As a method for producing the high molecular silicone compound of the present invention, for example, a phenolic hydroxyl group of a high molecular silicone compound having a repeating unit represented by the general formula (1) is added to an acid labile group represented by the general formula (6). And then, after isolation, a reaction with an alkenyl ether compound or a halogenated alkyl ether compound to crosslink with a crosslinking group having a C—O—C group in the molecule and / or between the molecules, By cross-linking with a cross-linking group having a C—O—C group in a molecule and / or between molecules by reaction with an alkylated alkyl ether compound, and after isolation, introducing an acid labile group represented by the general formula (6) And the reaction with an alkenyl ether compound or a halogenated alkyl ether compound and a compound represented by the general formula (6) Method of performing bulk introduction of acid labile groups are preferred. It is also possible to introduce an acid labile group represented by the general formula (7), a tertiary alkyl group, a trialkylsilyl group, an oxoalkyl group or the like into the polymer compound obtained as required. It is.

Specifically, as a first method, the formula (1 ′)
A method using a polymer compound having a repeating unit represented by the following formula, an alkenyl compound represented by the following general formula (I) or (II), and a compound represented by the following general formula (6a). A method using a polymer compound having a repeating unit represented by 1 ′), a halogenated alkyl ether compound represented by the following general formula (VI) or (VII), and a compound represented by the following general formula (6b) Can be

[0083]

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Here, x, y, z, p1, p2, q1,
q2 has the same meaning as above, and p1 + p2 + q1 + q
2 = 1.

The polysiloxanes of the above formulas (1) to (1 ′) can be obtained by the following synthesis method.

First, p-methoxybenzylchlorosilane or the like is hydrolyzed, and a polysiloxane comprising a repeating unit represented by the following general formula (8) obtained by further subjecting the hydrolyzed condensate to thermal condensation is used to terminate the main chain terminal of silanol. The polysiloxane comprising a repeating unit represented by the following general formula (9) is produced by trimethylsilylation for protecting the group. Here, for trimethylsilylation, it is preferable to dissolve the polysiloxane in an organic solvent such as toluene and use hexamethyldisilazane as a silylating agent. In this case, the reaction temperature is preferably 0 ° C. to room temperature, and the reaction time is preferably 2 to 5 hours. In this method, since the by-product ammonia does not remain in the reaction system after the trimethylsilylation, purification can be performed by stripping the reaction solvent under reduced pressure after the reaction, and the desired trimethylsilylation can be easily performed. There are advantages that can be. In addition, after dissolving in an organic solvent, trimethylsilylation can be performed by reacting with trimethylsilyl chloride in the presence of a base.However, in this case, it may be difficult to remove the resulting hydrochloride, and in particular, the hydrochloride may be difficult to remove. Is dissolved in water, the trimethylsilyl group is hydrolyzed, and silanol groups may be generated again in the polymer. Therefore, it is recommended to employ the above-mentioned method using hexamethyldisilazane. By reacting the polysiloxane composed of the repeating unit of the formula (8) with the hexamethyldisilazane or trimethyl chloride for protecting the silanol group at the terminal of the main chain, the polysiloxane (1) having very few residual silanol groups is obtained. Can be obtained.

Next, the polysiloxane (9) in which the hydrogen atom of the silanol group at the terminal of the main chain of the polysiloxane is trimethylsilylated, is converted from a methyl group whose phenolic hydroxyl group is protected with trimethylsilyl iodide to a trimethylsilyl group. By substitution, a polysiloxane comprising a repeating unit represented by the following general formula (10) is produced. In the trimethylsilylation reaction, trimethylsilyl iodide is dropped into the organic solvent, and the reaction temperature is adjusted to 20 to 30.
C. and the reaction time is preferably 8 to 10 hours.

Next, hydrolysis is carried out to remove the trimethylsilyl group protecting the phenolic hydroxyl group to generate a phenolic hydroxyl group, thereby obtaining a polysiloxane comprising a repeating unit represented by the following general formula (1). Here, as the hydrolysis conditions, known conditions for desilylation can be adopted. For example, water is added at a temperature of 30 to 45 ° C. while paying attention to heat generation under water cooling.

[0089]

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The above formulas (I), (II) and (6a)
In the formula, R ^2a represents a hydrogen atom or a linear group having 1 to 7 carbon atoms,
A branched or cyclic alkyl group, R ³ is a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, R ⁴
Represents a monovalent hydrocarbon group which may have a heteroatom having 1 to 18 carbon atoms, wherein R ^2a and R ³ , R ^2a and R ⁴ , R ³ and R ⁴
May form a ring, and when forming a ring, R ^2a represents a linear or branched alkylene group having 1 to 7 carbon atoms;
R ³ and R ⁴ each represent a linear or branched alkylene group having 1 to 8 carbon atoms.

R ^6a is a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to ⁷ carbon atoms, and R ⁷ is a C 1 to C 8 alkyl group.
Linear, but an alkyl group branched or cyclic, R ^6a
And R ⁷ may form a ring, and in the case of forming a ring, R ^6a is a linear or branched alkylene group having 1 to ⁷ carbon atoms, and R ⁷ is a linear alkylene group having 1 to 8 carbon atoms. It represents a branched or branched alkylene group. R ¹¹ represents a linear or branched alkylene group having 1 to 10 carbon atoms.

Further, in the vinyl ether compound represented by the formula (I) or (II), A is a c-valent (c is 2 to 8) aliphatic or alicyclic saturated hydrocarbon group having 1 to 50 carbon atoms. Represents an aromatic hydrocarbon group or a heterocyclic group,
Is -CO-O-, -NHCOO- or -NHCONH-
R ¹³ represents a linear or branched alkylene group having 1 to 10 carbon atoms, and d represents 0 or an integer of 1 to 10.

Specifically, the c-valent aliphatic or alicyclic saturated hydrocarbon group and aromatic hydrocarbon group of A are preferably C 1 to C 50, especially 1 to 40 carbon atoms such as O, NH, N
(CH _3), S, unsubstituted or hydroxyl or may be heteroatoms interposed such SO _2, a carboxyl group, an acyl group or a fluorine atom-substituted alkylene group, preferably having a carbon number of 6-5
0, especially 6 to 40 arylene groups, a group in which these alkylene groups and arylene groups are bonded, and a c ″ value (c ″ is 3 to 8) in which a hydrogen atom bonded to a carbon atom of each of the above groups is eliminated.
And a group in which this heterocyclic group is bonded to the above-mentioned hydrocarbon group.

Specific examples include the following as A.

[0095]

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[0096]

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[0097]

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[0098]

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The compound represented by the general formula (I) is described, for example, in Stephen. C. Lapin, Polymer
s Paint Color Journal. 17
9 (4237) and 321 (1988), that is, by a reaction between a polyhydric alcohol or polyhydric phenol and acetylene, or a reaction between a polyhydric alcohol or polyhydric phenol and a halogenated alkyl vinyl ether. Can be.

Specific examples of the compound of the formula (I) include ethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,2-propanediol divinyl ether, 1,3-propanediol divinyl ether and 1,3-butanediol divinyl ether. Vinyl ether, 1,4
-Butanediol divinyl ether, tetramethylene glycol divinyl ether, neopentyl glycol divinyl ether, trimethylolpropane trivinyl ether, trimethylolethane trivinyl ether, hexanediol divinyl ether, 1,4-cyclohexanediol divinyl ether, tetraethylene glycol divinyl ether, Pentaerythritol divinyl ether, pentaerythritol trivinyl ether,
Pentaerythritol tetravinyl ether, sorbitol tetravinyl ether, sorbitol pentavinyl ether, ethylene glycol diethylene vinyl ether, triethylene glycol diethylene vinyl ether, ethylene glycol dipropylene vinyl ether,
Triethylene glycol diethylene vinyl ether, trimethylolpropane triethylene vinyl ether, trimethylolpropane diethylene vinyl ether, pentaerythritol diethylene vinyl ether, pentaerythritol triethylene vinyl ether, pentaerythritol tetraethylene vinyl ether, and the following formulas (I-1) to (I-31) However, the present invention is not limited thereto.

[0101]

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[0102]

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[0103]

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[0104]

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[0105]

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On the other hand, when B is -CO-O-, the compound represented by the above general formula (II) can be produced by reacting a polyvalent carboxylic acid with a halogenated alkyl vinyl ether. Specific examples of the compound represented by the formula (II) when B is -CO-O- include diethylene vinyl ether terephthalate, diethylene vinyl ether phthalate, diethylene vinyl ether isophthalate, dipropylene vinyl ether phthalate, and dipropylene vinyl ether terephthalate. Diethylene vinyl ether isophthalate, diethylene vinyl ether maleate, diethylene vinyl ether fumarate, diethylene vinyl ether itaconate, and the like, but are not limited thereto.

The alkenyl ether group-containing compound preferably used in the present invention includes an alkenyl ether compound having an active hydrogen represented by the following general formula (III), (IV) or (V) and an isocyanate group. Alkenyl ether group-containing compounds synthesized by a reaction with a compound having the alkenyl ether group.

[0108]

Embedded image (R ^6a , R ⁷ and R ¹¹ have the same meaning as described above.)

B is -NHCO-O- or -NHCONH
In the case of-, as the compound having an isocyanate group represented by the above general formula (II), for example, the compounds described in Crosslinking Agent Handbook (published by Taiseisha, 1981) can be used. Specifically, triphenylmethane triisocyanate, diphenylmethane diisocyanate,
Polyisomer such as tolylene diisocyanate, dimer of 2,4-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-tolylene diisocyanate, polymethylene polyphenyl isocyanate, hexamethylene diisocyanate, etc. Polyisocyanate adducts such as isocyanate type, adducts of tolylene diisocyanate and trimethylolpropane, adducts of hexamethylene diisocyanate and water, adducts of xylene diisocyanate and trimethylolpropane, etc. be able to.
By reacting the above-mentioned isocyanate group-containing compound with an active hydrogen-containing alkenyl ether compound, various compounds having an alkenyl ether group at a terminal can be obtained. Such compounds are represented by the following formulas (II-1) to (II-1)
Examples shown in 1) can be cited, but are not limited thereto.

[0110]

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[0111]

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In the first method, the weight average molecular weight is from 5,000 to 50,000, and preferably p1 to 1 mol of the phenolic hydroxyl group of the high molecular silicone compound represented by the general formula (1 ′). Mole of the alkenyl ether compound represented by the general formula (I) or (II) and q
By reacting 1 mol of the compound represented by the general formula (6a), for example, the following general formulas (3a′-1) and (3a′-2)
Can be obtained.

[0113]

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[0114]

Embedded image In the above formula, x, y, z, p1, p2, q1, q
2, m, n, R ² , R ³ , R ⁴ , and Q are the same as above, except that m + n = x.

In the first method, the reaction solvent is
Aprotic polar solvents such as dimethylformamide, dimethylacetamide, tetrahydrofuran, and ethyl acetate are preferred, and they may be used alone or as a mixture of two or more.

As the acid of the catalyst, hydrochloric acid, sulfuric acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, pyridinium p-toluenesulfonic acid and the like are preferably used. It is preferable that the content is 0.1 to 10 mol% based on 1 mol of the phenolic hydroxyl group of the polymer compound represented by the formula (1 ′).

The reaction temperature is -20 to 100 ° C, preferably 0 to 60 ° C, and the reaction time is 0.2 to 1
00 hours, preferably 0.5 to 20 hours.

When the above reactions are carried out collectively without isolation,
The order in which the alkenyl ether compound represented by the general formula (I) or (II) and the compound represented by the general formula (6a) are added is not particularly limited. First, the compound represented by the general formula (6a) After the reaction has sufficiently proceeded, it is preferable to add the alkenyl ether compound represented by the general formula (I) or (II). For example, the alkenyl ether compound represented by the general formula (I) or (II) and the compound represented by the general formula (6a) are added simultaneously, or the alkenyl ether compound represented by the general formula (I) or (II) is added first. When added, the compound represented by the general formula (I) or (II)
In some cases, a part of the reaction points of the alkenyl ether compound represented by the formula (1) is hydrolyzed by water in the reaction system, the structure of the produced polymer compound becomes complicated, and the control of physical properties may be difficult.

[0119]

Embedded image (Where x, y, z, p1, p2, q1, q2, R ^2a ,
R ³ , R ⁴ , R ⁶ , R ⁷ , R ¹¹ , A, B, c, and d each have the same meaning as described above, and Z represents a halogen atom (CI, B
r and I). )

The compounds of the above formulas (VI) and (VII) and the compound of the formula (6b) are the same as the compounds of the above formulas (I) and (II) and the compound of the formula (6a) except for hydrogen chloride and hydrogen bromide. Alternatively, it can be obtained by reacting hydrogen iodide.

In the second method, the weight average molecular weight is 5,0
00 to 50,000, preferably of the general formula (1 ′)
In the high molecular compound having a repeating unit represented by the formula (1), 1 mol of the phenolic hydroxyl group is added in an amount of 1 mol of the general formula (V
The halogenated alkyl ether compound represented by the formula (I) or (VII) is reacted with q1 mol of the compound represented by the general formula (6b) to form, for example, the above formula (3a′-1), (3
The polymer compound represented by a'-2) can be obtained.

The above production method is preferably carried out in a solvent in the presence of a base. As the reaction solvent, aprotic polar solvents such as acetonitrile, acetone, dimethylformamide, dimethylacetamide, tetrahydrofuran and dimethylsulfoxide are preferable.
A mixture of more than one species may be used.

The base is preferably triethylamine, pyridine, diisopropylamine, potassium carbonate or the like. The amount of the base used is 1 mol per 1 mol of the phenolic hydroxyl group of the polymer compound represented by the general formula (1 ′) to be reacted. It is preferably at least 2 times, particularly preferably at least 5 times.

The reaction temperature is -50 to 100 ° C, preferably 0 to 60 ° C, and the reaction time is 0.5 to 1
00 hours, preferably 1 to 20 hours.

As described above, the polymer having the repeating unit represented by the formula (1 ') is reacted with the compound represented by the formula (6a) or (6b) to obtain a compound represented by the following formula (11). After having been obtained, it may be isolated and then crosslinked using a compound of formula (I), (II) or (VI), (VII).

[0126]

Embedded image (Wherein, R ^{2 to} R ⁴ , x, y, z, m, n, p1, p2,
q1 and q2 each have the same meaning as described above. )

The polymer compound represented by, for example, the formula (3a′-1) or (3a′-2) obtained by the above first or second method may be added to the original formula (1 ′) if necessary. ) Is reacted with q2 mol of a dialkyl dicarbonate compound, an alkoxycarbonylalkyl halide or the like with respect to 1 mol of the phenolic hydroxyl group of the polymer compound represented by the general formula (6).
Or by reacting a tertiary alkyl halide, a trialkylsilyl halide, an oxoalkyl compound, or the like, for example, with the general formula (3b′-1):
A polymer compound represented by (3b′-2) can be obtained.

[0128]

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[0129]

Embedded image (Wherein, R ^{2 to} R ⁵ , Q, x, y, z, m, n, p1, p
2, q1 and q2 each have the same meaning as described above. )

The method for introducing the acid labile group of the above formula (7) is as follows.
It is preferable to carry out the reaction in a solvent in the presence of a base.

Examples of the reaction solvent include acetonitrile, acetone, dimethylformamide, dimethylacetamide,
Aprotic polar solvents such as tetrahydrofuran and dimethylsulfoxide are preferred, and they may be used alone or as a mixture of two or more.

As the base, triethylamine, pyridine, imidazole, diisopropylamine, potassium carbonate and the like are preferable, and the amount of the base is based on 1 mol of the phenolic hydroxyl group of the original polymer compound represented by the general formula (1 ′). It is preferably at least 1 mol times, particularly preferably at least 5 mol times.

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

Examples of the dialkyl dicarbonate compound include di-tert-butyl dicarbonate and di-tert-amyl dicarbonate. Examples of the alkoxycarbonylalkyl halide include tert-butoxycarbonyl methyl chloride and
tert-amyloxycarbonylmethyl chloride, t
tert-butoxycarbonylmethyl bromide, ter
t-butoxycarbonylethyl chloride, ethoxyethoxycarbonylmethyl chloride, ethoxyethoxycarbonylmethyl chloride, tetrahydropyranyloxycarbonylmethyl chloride, tetrahydropyranyloxycarbonylmethyl chloride, tetrahydrofuranyloxycarbonylmethyl chloride, tetrahydrofuranyloxycarbonylmethyl bromide And trialkylsilyl halides such as trimethylsilyl chloride, triethylsilyl chloride and dimethyl-tert-butylsilyl chloride.

The polymer compound represented by the general formula (3a′-1) or (3a′-2) obtained by the above first or second method may be added to the original compound represented by the general formula (1) if necessary. The tertiary alkylation or oxoalkylation can be performed by reacting q2 mol of a tertiary alkylating agent and an oxoalkyl compound with respect to 1 mol of the phenolic hydroxyl group of the polymer compound represented by ').

The above method is preferably carried out in a solvent in the presence of an acid. As the reaction solvent, dimethylformamide, dimethylacetamide, tetrahydrofuran, aprotic polar solvents such as ethyl acetate are preferred,
They may be used alone or in combination of two or more.

As the acid of the catalyst, hydrochloric acid, sulfuric acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, pyridinium p-toluenesulfonate and the like are preferable. It is preferably 0.1 to 10 mol% with respect to 1 mol of the phenolic hydroxyl group of the polymer compound represented by the formula (1 ′).

The reaction temperature is -20 to 100 ° C, preferably 0 to 60 ° C, and the reaction time is 0.2 to 1
00 hours, preferably 0.5 to 20 hours.

As the tertiary alkylating agent, isobutene, 2
-Methyl-1-butene, 2-methyl-2-butene and the like, and the oxoalkyl compound is α-angelicalactone, 2-cyclohexen-1-one, 5,6-
And dihydro-2H-pyran-2-one.

The formulas (3a'-1) and (3a'-
2) The polymer compound having a repeating unit represented by the following general formula (3c′-1) or (3c′-2) directly without passing through the polymer compound represented by the formula (7) An unstable group, a tertiary alkyl group, a trialkylsilyl group,
After the introduction of an oxoalkyl group or the like, an acid labile group represented by the general formula (6) can be introduced as necessary.

[0141]

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[0142]

Embedded image (In the formula, Q, x, y, z, p1, p2, q1, and q2 each have the same meaning as described above.)

In the high molecular silicone compound of the present invention, the acid labile group of R ¹ is not limited to one type, and two or more types can be introduced. In this case, q1 mol of the acid labile group is introduced as described above with respect to 1 mol of all hydroxyl groups of the polymer compound of the formula (1 ′), and then a different acid labile group is introduced in the same manner as described above. By introducing p2 mol of the above, a polymer compound in which two or more such acid labile groups are introduced or more operations are appropriately introduced can be obtained.

The polymer silicone compound of the present invention is effective as a base polymer of a chemically amplified positive resist material. The present invention provides a chemically amplified positive resist material containing the following components which uses this polymer compound as a base polymer. I will provide a. (A) Organic solvent (B) High molecular silicone compound as base resin (C) Acid generator Further if necessary (D) Dissolution controller (E) Basic compound (F) Base resin different from component (B) (G) acetylene alcohol derivative

The organic solvent (A) used in the present invention may be any organic solvent in which the acid generator, the base resin, the dissolution controlling agent and the like can be dissolved. Such organic solvents include, for example, cyclohexanone, methyl-2
Ketones such as -n-amyl ketone, alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, propylene glycol monomethyl ether, ethylene glycol Monomethyl ether,
Ethers such as propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate,
Methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, t-propionic acid
tert-butyl, propylene glycol-mono-ter
Esters such as t-butyl ether acetate are mentioned, and one of these can be used alone or a mixture of two or more thereof, but is not limited thereto. In the present invention, among these organic solvents, in addition to diethylene glycol dimethyl ether and 1-ethoxy-2-propanol, which have the highest solubility of the acid generator in the resist component, propylene glycol monomethyl ether acetate as a safe solvent and a mixture thereof Solvents are preferably used.

The amount of the organic solvent used is 200 to 100 parts (parts by weight, hereinafter the same) of the base resin of the component (B).
1,000 parts, especially 400 to 800 parts, are suitable.

The acid generator of the component (C) includes an onium salt of the following general formula (12), a diazomethane derivative of the formula (13), a glyoxime derivative of the formula (14), a β-ketosulfone derivative, a disulfone derivative, and nitrobenzyl. Sulfonate derivatives, sulfonic acid ester derivatives, imido-yl sulfonate derivatives, and the like.

(R ³⁰ ) _b M ⁺ K ⁻ (12) (where R ³⁰ is a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms or carbon number Represents 7 to 12 aralkyl groups, M ⁺ represents iodonium or sulfonium, K ⁻ represents a non-nucleophilic counter ion, and b is 2 or 3.)

As the alkyl group for R ^30, a methyl group, an ethyl group, a propyl group, a butyl group, a cyclohexyl group, a 2-
An oxocyclohexyl group, a norbornyl group, an adamantyl group and the like can be mentioned. As the aryl group, a phenyl group,
p-methoxyphenyl group, m-methoxyphenyl group, o
-Methoxyphenyl group, ethoxyphenyl group, p-te
an alkoxyphenyl group such as an rt-butoxyphenyl group, an m-tert-butoxyphenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group,
Ethylphenyl group, 4-tert-butylphenyl group,
Examples thereof include an alkylphenyl group such as a 4-butylphenyl group and a dimethylphenyl group. Examples of the aralkyl group include a benzyl group and a phenethyl group. K ^- a non-nucleophilic counter chloride ions as the ion, halide ions such as bromide ion, triflate, 1,1,1-trifluoroethane sulfonate, fluoroalkyl sulfonate such as nonafluorobutanesulfonate, tosylate, benzenesulfonate , 4-fluorobenzenesulfonate, arylsulfonates such as 1,2,3,4,5-pentafluorobenzenesulfonate, and alkylsulfonates such as mesylate and butanesulfonate.

[0150]

Embedded image (However, R ³¹ and R ³² are a linear, branched or cyclic alkyl group or halogenated alkyl group having 1 to 12 carbon atoms, an aryl group or halogenated aryl group having 6 to 12 carbon atoms, or a C ⁷ to C 12 12 represents an aralkyl group)

Examples of the alkyl group for R ³¹ and R ³² include a methyl group, an ethyl group, a propyl group, a butyl group, an amyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group and an adamantyl group. Examples of the halogenated alkyl group include a trifluoromethyl group, a 1,1,1-trifluoroethyl group, a 1,1,1-trichloroethyl group, a nonafluorobutyl group, and the like. Examples of the aryl group include phenyl, p-methoxyphenyl, m-methoxyphenyl, o-methoxyphenyl, ethoxyphenyl, p-tert-butoxyphenyl, and m-tert.
An alkoxyphenyl group such as -butoxyphenyl group, 2-
Examples thereof include an alkylphenyl group such as a methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, an ethylphenyl group, a 4-tert-butylphenyl group, a 4-butylphenyl group, and a dimethylphenyl group. Examples of the halogenated aryl group include a fluorobenzene group, a chlorobenzene group, a 1,2,3,4,5-pentafluorobenzene group, and the like. Examples of the aralkyl group include a benzyl group and a phenethyl group.

[0152]

Embedded image (However, R ³³ , R ³⁴ , and R ³⁵ are linear having 1 to 12 carbon atoms;
It represents a branched or cyclic alkyl group or a halogenated alkyl group, an aryl group having 6 to 12 carbon atoms, an aryl halide group or an aralkyl group having 7 to 12 carbon atoms. Also,
R ³⁴ and R ³⁵ may combine with each other to form a cyclic structure, and when forming a cyclic structure, R ³⁴ and R ³⁵ each represent a linear or branched alkylene group having 1 to 6 carbon atoms. . )

As the alkyl group, halogenated alkyl group, aryl group, halogenated aryl group and aralkyl group represented by R ³³ , R ³⁴ and R ³⁵ , the same groups as those described for R ³¹ and R ³² can be mentioned. The alkylene group for R ³⁴ and R ³⁵ includes a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group and the like.

More specifically, for example, diphenyliodonium trifluoromethanesulfonate, phenyliodonium trifluoromethanesulfonate (p-tert-butoxyphenyl), diphenyliodonium p-toluenesulfonate, p-toluenesulfonic acid (p-tert-
(Butoxyphenyl) phenyliodonium, triphenylsulfonium trifluoromethanesulfonate, trifluoromethanesulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, bis (p-tert-butoxyphenyl) phenylsulfonium trifluoromethanesulfonate, tris trifluoromethanesulfonate (P-tert-butoxyphenyl) sulfonium,
triphenylsulfonium p-toluenesulfonate, p
-(P-tert-butoxyphenyl) diphenylsulfonium toluenesulfonate, bis (p-tert-butoxyphenyl) phenylsulfonium p-toluenesulfonate, tris (p-tert-toluenesulfonate)
(t-butoxyphenyl) sulfonium, triphenylsulfonium nonafluorobutanesulfonate, triphenylsulfonium butanesulfonate, trimethylsulfonium trifluoromethanesulfonate, trimethylsulfonium p-toluenesulfonate, cyclohexylmethyl trifluoromethanesulfonate (2-oxocyclohexyl) Sulfonium, cyclohexylmethyl p-toluenesulfonate (2-oxocyclohexyl) sulfonium, dimethylphenylsulfonium trifluoromethanesulfonate, dimethylphenylsulfonium p-toluenesulfonate, dicyclohexylphenylsulfonium trifluoromethanesulfonate, dicyclohexylphenylsulfonium p-toluenesulfonate Onium salts such as bis (benze) Sulfonyl) diazomethane, bis (p- toluenesulfonyl) diazomethane, bis (xylene sulfonyl) diazomethane, bis (cyclohexyl sulfonyl) diazomethane, bis (cyclopentyl sulfonyl) diazomethane, bis (n- butylsulfonyl)
Diazomethane, bis (isobutylsulfonyl) diazomethane, bis (sec-butylsulfonyl) diazomethane, bis (n-propylsulfonyl) diazomethane, bis (isopropylsulfonyl) diazomethane, bis (t
tert-butylsulfonyl) diazomethane, bis (n-
Amylsulfonyl) diazomethane, bis (isoamylsulfonyl) diazomethane, bis (sec-amylsulfonyl) diazomethane, bis (tert-amylsulfonyl) diazomethane, 1-cyclohexylsulfonyl-1
-(Tert-butylsulfonyl) diazomethane, 1-
Diazomethane derivatives such as cyclohexylsulfonyl-1- (tert-amylsulfonyl) diazomethane and 1-tert-amylsulfonyl-1- (tert-butylsulfonyl) diazomethane; bis-o- (p-toluenesulfonyl) -α-dimethylglyoxime , Bis-o-
(P-toluenesulfonyl) -α-diphenylglyoxime, bis-o- (p-toluenesulfonyl) -α-dicyclohexylglyoxime, bis-o- (p-toluenesulfonyl) -2,3-pentanedione glyoxime, Bis-o- (p-toluenesulfonyl) -2-methyl-3,4-pentanedione glyoxime, bis-o-
(N-butanesulfonyl) -α-dimethylglyoxime, bis-o- (n-butanesulfonyl) -α-diphenylglyoxime, bis-o- (n-butanesulfonyl) -α-dicyclohexylglyoxime, bis-o −
(N-butanesulfonyl) -2,3-pentanedione glyoxime, bis-o- (n-butanesulfonyl) -2
-Methyl-3,4-pentanedione glyoxime, bis-o- (methanesulfonyl) -α-dimethylglyoxime, bis-o- (trifluoromethanesulfonyl) -α
-Dimethylglyoxime, bis-o- (1,1,1-trifluoroethanesulfonyl) -α-dimethylglyoxime, bis-o- (tert-butanesulfonyl) -α
-Dimethylglyoxime, bis-o- (perfluorooctanesulfonyl) -α-dimethylglyoxime, bis-o- (cyclohexanesulfonyl) -α-dimethylglyoxime, bis-o- (benzenesulfonyl) -α-
Dimethylglyoxime, bis-o- (p-fluorobenzenesulfonyl) -α-dimethylglyoxime, bis-
o- (p-tert-butylbenzenesulfonyl) -α
Glyoxime derivatives such as -dimethylglyoxime, bis-o- (xylenesulfonyl) -α-dimethylglyoxime, bis-o- (camphorsulfonyl) -α-dimethylglyoxime, 2-cyclohexylcarbonyl-2
Β-ketosulfone derivatives such as-(p-toluenesulfonyl) propane and 2-isopropylcarbonyl-2- (p-toluenesulfonyl) propane; disulfone derivatives such as diphenyldisulfone and dicyclohexyldisulfone; 2,6-dinitrop-toluenesulfonate Nitrobenzylsulfonate derivatives such as benzyl and 2,4-dinitrobenzyl p-toluenesulfonate;
Tris (methanesulfonyloxy) benzene, 1,2,2
Sulfonate derivatives such as 3-tris (trifluoromethanesulfonyloxy) benzene and 1,2,3-tris (p-toluenesulfonyloxy) benzene, phthalimido-yl-triflate, phthalimido-yl-
Tosylate, 5-norbornene-2,3-dicarboximido-yl-triflate, 5-norbornene-2,
Imido-yl-sulfonate derivatives such as 3-dicarboximido-yl-tosylate and 5-norbornene-2,3-dicarboximido-yl-n-butylsulfonate; and triphenylsulfonium trifluoromethanesulfonate; Triphenylmethanesulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, trifluoromethanesulfonic acid tris (p-
Onium such as tert-butoxyphenyl) sulfonium, triphenylsulfonium p-toluenesulfonate, diphenylsulfonium p-toluenesulfonate (p-tert-butoxyphenyl), and tris (p-tert-butoxyphenyl) sulfonium p-toluenesulfonate Salt, bis (benzenesulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (n-butylsulfonyl) diazomethane, bis (isobutylsulfonyl) diazomethane, bis (sec-butylsulfonyl) diazomethane, Bis (n-propylsulfonyl) diazomethane, bis (isopropylsulfonyl)
Diazomethane derivatives such as diazomethane and bis (tert-butylsulfonyl) diazomethane; bis-o- (p-
Glyoxime derivatives such as toluenesulfonyl) -α-dimethylglyoxime and bis-o- (n-butanesulfonyl) -α-dimethylglyoxime are preferably used. In addition, the said acid generator can be used individually by 1 type or in combination of 2 or more types. The onium salt is excellent in the effect of improving the rectangularity, and the diazomethane derivative and the glyoxime derivative are excellent in the standing wave reducing effect. However, by combining the two, fine adjustment of the profile can be performed.

The amount of the acid generator is preferably 0.5 to 15 parts, more preferably 1 to 100 parts of the base resin.
~ 8 parts. If the amount is less than 0.5 part, the sensitivity may be poor. If the amount is more than 15 parts, the resolution of the resist material may decrease due to a decrease in the alkali dissolution rate. Performance may be reduced.

The resist material of the present invention is also suitable as a three-component system containing a dissolution controlling agent (D).
The dissolution controlling agent (D) may be a low molecular weight compound or a high molecular weight compound as long as it has one or more acid labile groups in the molecule. Dissolution control agents can be used. Here, examples of the acid labile group include those similar to the general formulas (6) and (7). As such a dissolution controlling agent (D), for example, the hydroxyl group of bisphenol A is replaced with tert-B
Examples of the compound include an oc-converted compound, and a compound in which phloroglucin and tetrahydroxybenzophenone are tert-Boc-modified.

As the dissolution controlling agent (D), a hydrogen atom of the phenolic hydroxyl group of a compound having an average molecular weight of 100 to 1,000, preferably 150 to 800 and having two or more phenolic hydroxyl groups in the molecule is used. A compound substituted by an acid labile group at a ratio of 0 to 100 mol% on average as a whole is blended. That is, the substitution rate of the hydrogen atom of the phenolic hydroxyl group by the acid labile group is 0 mol% or more, preferably 30 mol% or more of the entire phenolic hydroxyl group, and the upper limit is 100 mol%, more preferably. Is 8
0 mol%.

In this case, the phenolic hydroxyl group is
Compounds having one or more of the following formulas (i) to (xi)
Are preferred.

[0159]

Embedded image

[0160]

Embedded image

[0161]

Embedded image (Where R ⁵¹ and R ⁵² are each a hydrogen atom or a linear or branched alkyl group or alkenyl group having 1 to 8 carbon atoms, and R ⁵³ is a hydrogen atom or a linear chain having 1 to 8 carbon atoms. Or branched alkyl or alkenyl group, or-
(R ⁵⁷ ) _h —COOH, and R ⁵⁴ is — (CH ₂ ) _i —
(I = 2 to 10), an arylene group having 6 to 10 carbon atoms, a carbonyl group, a sulfonyl group, an oxygen atom or a sulfur atom, R
⁵⁵ is an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, a carbonyl group, a sulfonyl group, an oxygen atom or a sulfur atom, and ^R56 is a hydrogen atom or a linear or branched chain having 1 to 8 carbon atoms. An alkyl group, an alkenyl group, a phenyl group or a naphthyl group each substituted with a hydroxyl group,
⁵⁷ is a linear or branched alkylene group having 1 to 10 carbon atoms. J is an integer of 0 to 5, and h and u are 0 or 1. s, t, s ′, t ′, s ″, and t ″ are s + t = 8, s ′ + t ′ = 5, and s ″ + t ″ =
It is a number satisfying 4 and having at least one hydroxyl group in each phenyl skeleton. α is the formula (viii),
It is a number that makes the molecular weight of the compound (ix) 100 to 1,000. )

In the above formula, R ⁵¹ and R ⁵² are, for example, hydrogen atom, methyl group, ethyl group, butyl group, propyl group, ethynyl group, cyclohexyl group, and R ⁵³ are, for example, R
⁵¹ , the same as R ⁵² , or —COOH, —CH ₂
COOH and R ⁵⁴ include, for example, an ethylene group, a phenylene group, a carbonyl group, a sulfonyl group, an oxygen atom and a sulfur atom, and R ⁵⁵ includes, for example, a methylene group or R ⁵⁴
Examples of ^R56 include a hydrogen atom, a methyl group, an ethyl group, a butyl group, a propyl group, an ethynyl group, a cyclohexyl group, a phenyl group substituted with a hydroxyl group, a naphthyl group, and the like.

Here, the acid labile group of the dissolution controlling agent includes a group represented by the above general formula (6) and a group represented by the above general formula (7)
Or a tertiary alkyl group having 4 to 20 carbon atoms, a trialkylsilyl group having 1 to 6 carbon atoms each, or an oxoalkyl group having 4 to 20 carbon atoms.

The compounding amount of the above-mentioned dissolution controlling agent is as follows.
It is 0 to 50 parts, preferably 5 to 50 parts, more preferably 10 to 30 parts with respect to 00 parts, and can be used alone or in combination of two or more. If the amount is less than 5 parts, the resolution may not be improved. If the amount is more than 50 parts, the pattern may be reduced in film thickness and the resolution may be reduced.

The dissolution controlling agent as described above can be synthesized by chemically reacting a compound having a phenolic hydroxyl group with an acid labile group as in the case of the base resin.

The resist composition of the present invention may be a compound having a weight average molecular weight of less than 1,000 and having a phenolic hydroxyl group in the molecule as another dissolution controlling agent instead of or in addition to the dissolution controlling agent. The hydrogen atom of the phenolic hydroxyl group is occupied by an acid labile group on average of 0% or more.
A partially substituted compound can be blended at a ratio of 0% or less.

In this case, as the compound in which the hydrogen atom of the phenolic hydroxyl group is partially substituted with such an acid labile group,
One or more compounds selected from compounds having a repeating unit represented by the following general formula (15) and having a weight average molecular weight of more than 1,000 and not more than 3,000 are preferred.

[0168]

Embedded image (Wherein, R ¹ represents an acid labile group, and v and w are numbers satisfying 0 ≦ v / (v + w) ≦ 0.6, respectively)

Here, the acid labile group of the dissolution controlling agent includes a group represented by the general formula (6), a group represented by the general formula (7), and a tertiary alkyl group having 4 to 20 carbon atoms. And each alkyl group includes a trialkylsilyl group having 1 to 6 carbon atoms and an oxoalkyl group having 4 to 20 carbon atoms.

The compounding amount of the above-mentioned another dissolution controlling agent is based on the total amount of the dissolution controlling agent and the base resin 10
0 to 50 parts, especially 0 to 30 parts, preferably 1 to 0 parts
It is preferable that the amount be in a range such that at least one part is used.

The above-mentioned other dissolution controlling agent can be synthesized by chemically reacting a compound having a phenolic hydroxyl group with an acid labile group in the same manner as in the base resin.

As the dissolution controlling agent (D), a silicone compound can be preferably used so as not to impair oxygen plasma etching resistance. As the dissolution controlling agent for the silicone compound, use is made of a silicone compound represented by the following general formulas (16) to (18) in which a carboxyl group or a hydroxyl group is protected with a tert-butyl group or a tert-butoxycarbonylmethyl group. Can be.

[0173]

Embedded image (Wherein, R ¹² represents a methyl group or a phenyl group, R ¹³ represents a carboxyethyl group or a p-hydroxyphenylalkyl group. X represents a trimethylsilyl group, a triphenylsilyl group, or —SiR ¹² R ¹³ (R ¹² , R ¹³ has the same meaning as described above), e is an integer of 0 to 50, f is 1 to
Integer of 50 and g show the integer of 3-10. )

The silicone compounds of the formulas (16) to (18) in which the carboxyl group or hydroxyl group is protected with an alkali-soluble group (tert-butyl group or tert-butoxycarbonylmethyl group) include The compounds of the following groups A to C are exemplified. Here, Me represents a methyl group, and t-Bu represents a tert-butyl group.

[0175]

Embedded image

[0176]

Embedded image

[0177]

Embedded image

When the dissolution controlling agent of the silicone compound is used, the content is from 0 to 6 based on 100 parts of the base resin.
It is preferably 0 parts, particularly preferably 0 to 50 parts. If it exceeds 60 parts, the resistance of the resist film to oxygen plasma etching is remarkably reduced, so that the resist film may not be usable as a two-layer resist.

The resist composition of the present invention further comprises (E)
A basic compound can be blended as a component.

As the basic compound to be added as the (E) additive, a compound capable of suppressing the diffusion rate when the acid generated from the acid generator diffuses into the resist film is suitable. Incorporation of a basic compound suppresses the diffusion rate of acid in the resist film to improve resolution, suppresses sensitivity changes after exposure, reduces substrate and environment dependency, reduces exposure margin and pattern Profiles and the like can be improved.

Examples of such a basic compound include:
Primary, secondary, tertiary aliphatic amines, mixed amines,
Aromatic amines, heterocyclic amines, nitrogen-containing compounds having a carboxy group, nitrogen-containing compounds having a sulfonyl group,
Examples include a nitrogen-containing compound having a hydroxy group, a nitrogen-containing compound having a hydroxyphenyl group, an alcoholic nitrogen-containing compound, an amide derivative, and an imide derivative.

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

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

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

Further, basic compounds represented by the following general formulas (19) and (20) can be blended.

[0186]

Embedded image (Wherein, R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁷ and R ⁴⁸ are each independently a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms, R ⁴⁴ , R ⁴⁵ and R ⁴⁶⁾ , R ⁴⁹ and R ⁵⁰ are hydrogen atoms,
An alkyl group or an amino group having 1 to 20 carbon atoms, R ⁴⁴
And R ⁴⁵ , R ⁴⁵ and R ⁴⁶ , R ⁴⁴ and R ⁴⁶ , R ⁴⁴ and R ⁴⁵ and R ⁴⁶ ,
R ⁴⁹ and R ⁵⁰ may be combined with each other to form a ring.
S, T, and U each represent an integer of 0 to 20. However,
When S, T, U = 0, R ⁴⁴ , R ⁴⁵ , R ⁴⁶ , R ⁴⁹ , R ⁵⁰
Does not contain a hydrogen atom. )

The alkylene group represented by R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁷ and R ⁴⁸ has 1 to 20 carbon atoms, preferably 1 carbon atom.
-10, more preferably 1-8, and specifically, methylene, ethylene, n-propylene, isopropylene, n-butylene, isobutylene, n-
Examples include a pentylene group, an isopentylene group, a hexylene group, a nonylene group, a decylene group, a cyclopentylene group, and a cyclohexylene group.

The alkyl group of R ⁴⁴ , R ⁴⁵ , R ⁴⁶ , R ⁴⁹ and R ⁵⁰ has 1 to 20 carbon atoms, preferably 1 to 20 carbon atoms.
8, more preferably 1 to 6, which may be linear, branched, or cyclic. Specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, hexyl, nonyl, decyl, dodecyl Group, tridecyl group, cyclopentyl group, cyclohexyl group and the like.

Furthermore, R ⁴⁴ and R ⁴⁵ , R ⁴⁵ and R ⁴⁶ , R ⁴⁴ and R ^46
46, if R ⁴⁴ and R ⁴⁵ and R ^46, R ⁴⁹ and R ⁵⁰ form rings, the number of carbon atoms in the ring is 1 to 20, more preferably 1 to
8, more preferably 1 to 6, and in these rings, an alkyl group having 1 to 6, particularly 1 to 4 carbon atoms may be branched.

S, T and U are each an integer of 0 to 20, more preferably 1 to 10, and further preferably an integer of 1 to 8.

Specific examples of the compounds of the above (19) and (20) include tris {2- (methoxymethoxy) ethyl}
Amine, tris {2- (methoxyethoxy) ethyl} amine, tris [2-{(2-methoxyethoxy) methoxy} ethyl] amine, tris {2- (2-methoxyethoxy) ethyl} amine, tris {2- ( 1-methoxyethoxy) ethyl} amine, tris {2- (1-ethoxyethoxy) ethyl} amine, tris {2- (1-ethoxypropoxy) ethyl} amine, tris [2-{(2-
Hydroxyethoxy) ethoxydiethyl] amine, 4,
7,13,16,21,24-hexaoxa-1,10
-Diazabicyclo [8.8.8] hexacosan, 4,
7,13,18-tetraoxa-1,10-diazabicyclo [8.5.5] eicosan, 1,4,10,13-
Tetraoxa-7,16-diazabicyclooctadecane, 1-aza-12-crown-4, 1-aza-15-
Crown-5, 1-aza-18-crown-6 and the like. In particular, tertiary amines, aniline derivatives, pyrrolidine derivatives, pyridine derivatives, quinoline derivatives, amino acid derivatives, nitrogen-containing compounds having a hydroxy group, nitrogen-containing compounds having a hydroxyphenyl group, alcoholic nitrogen-containing compounds, amide derivatives, imide derivatives, Tris ｛2-
(Methoxymethoxy) ethyl {amine, tris} (2-
(2-methoxyethoxy) ethyldiamine, tris [2
-{(2-methoxyethoxy) methyl} ethyl] amine, 1-aza-15-crown-5 and the like are preferred.

The above basic compounds can be used alone or in combination of two or more. The compounding amount is 0 to 2 parts, especially 0.0 to 2 parts with respect to 100 parts of the base resin.
A mixture of 1 to 1 part is preferred. If the amount exceeds 2 parts, the sensitivity may be too low.

As the base resin other than the crosslinked polymer compound relating to the component (B) of the component (F), in particular, a resin having a weight average molecular weight of 3 having a repeating unit represented by the following general formula (21) is preferred. 2,000 to 300,000 high molecular compounds are preferably used.

Further, by blending the component (F), the dimension of the pattern and the shape of the pattern can be arbitrarily controlled, which is advantageous.

[0195]

Embedded image

In the above formula, Me, R ² -R ⁴ , y, z
Each represents the same meaning as described above, and R ¹ is an acid labile group different from the above formula (6), for example, a group represented by the above formula (7), a tertiary alkyl group having 4 to 20 carbon atoms, Each alkyl group is a trialkylsilyl group having 1 to 6 carbon atoms, an oxoalkyl group having 4 to 20 carbon atoms, or the like.

E and f are each 0 or a positive number;
f may be 0 at the same time, g is a positive number, and e +
f + g = 1. These composition ratios are 0 ≦ e / (e + f
+ G) ≦ 0.5, preferably 0.1 ≦ e / (e + f +
g) ≦ 0.4, 0 ≦ f / (e + f + g) ≦ 0.5, preferably 0 ≦ f / (e + f + g) ≦ 0.2, 0.4 ≦ g /
(E + f + g) ≦ 0.9, preferably 0.6 ≦ g / (e
+ F + g) ≦ 0.8. The ratio of e to the whole (e + f + g, the same applies hereinafter) exceeds 0.5, the ratio of f to the whole exceeds 0.5, and the ratio of g to the whole is 0.9
Or the ratio of g to the whole is less than 0.4, the contrast of the alkali dissolution rate becomes small and the resolution may be deteriorated. By appropriately selecting the values of e, f, and g within the above range, the dimension of the pattern and the shape of the pattern can be arbitrarily controlled.

Such a high molecular compound has a weight average molecular weight of 3,000 to 300,000, preferably 5,000.
It must be between 0 and 30,000. If the weight average molecular weight is less than 3,000, the resist material will have poor heat resistance. If it exceeds 300,000, the alkali solubility will be reduced and the resolution will be poor.

The compounding ratio of the base resin (F) to the base resin (crosslinked polymer compound) of the component (B) is preferably 0: 100 to 90:10 by weight. In particular, 0: 100 to 50:50 is preferable. If the amount of the base resin (F) is greater than the above weight ratio, the desired effect of the base resin (crosslinked polymer compound) of the component (B) may not be obtained.

The resist composition of the present invention further comprises (G)
An acetylene alcohol derivative can be blended as a component, which can improve the storage stability.

As the acetylene alcohol derivative, those represented by the following formulas (22) and (23) can be suitably used.

[0202]

Embedded image (Wherein, R ⁷¹ , R ⁷² , R ⁷³ , R ⁷⁴ , and R ⁷⁵ are each a hydrogen atom or a linear, branched, or cyclic alkyl group having 1 to 8 carbon atoms, and X and Y are 0 or Indicates a positive number and satisfies the following values: 0 ≦ X ≦ 30, 0 ≦ Y ≦ 30, 0 ≦ X + Y ≦
40. )

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

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

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

The surfactant is preferably a nonionic surfactant, and is preferably a perfluoroalkylpolyoxyethylene ethanol, a fluorinated alkyl ester, a perfluoroalkylamine oxide, a perfluoroalkylEO adduct, or a fluorine-containing organosiloxane-based surfactant. And the like. For example, Florard "FC-430",
"FC-431" (all are Sumitomo 3M Limited)
), Surflon "S-141", "S-145" (all manufactured by Asahi Glass Co., Ltd.), Unidyne "DS-40"
1 "," DS-403 "," DS-451 "(all manufactured by Daikin Industries, Ltd.), MegaFac" F-815 "
1 "(manufactured by Dainippon Ink Industries, Ltd.)," X-70-09 "
2 "," X-70-093 "(all manufactured by Shin-Etsu Chemical Co., Ltd.) and the like. Preferably, Florado “FC-430” (manufactured by Sumitomo 3M Limited),
"X-70-093" (manufactured by Shin-Etsu Chemical Co., Ltd.).

A pattern can be formed using the chemically amplified positive resist material of the present invention by employing a known lithography technique. For example, a pattern such as spin coating is applied onto a substrate such as a silicon wafer. The film is applied so as to have a thickness of 0.5 to 2.0 μm, and is prebaked on a hot plate at 60 to 150 ° C. for 1 to 10 minutes, preferably at 80 to 120 ° C. for 1 to 5 minutes. Next, a mask for forming a target pattern is held over the resist film, and a deep ultraviolet ray having a wavelength of 300 nm or less, an excimer laser, a high energy ray such as an X-ray or an electron beam is exposed at a dose of about 1 to 200 mJ / cm ² . Preferably 10
After irradiating to about 100 mJ / cm ² , post-exposure bake (PEB) is performed on a hot plate at 60 to 150 ° C. for 1 to 5 minutes, preferably 80 to 120 ° C. for 1 to 3 minutes. Further, using a developer of an aqueous alkali solution such as 0.1 to 5%, preferably 2 to 3% tetramethylammonium hydroxide (TMAH),
Dipping for 0.1 to 3 minutes, preferably 0.5 to 2 minutes (d
ip) method, paddle method, spray method (sp
(ray) method to form a target pattern on the substrate by performing development. The material of the present invention is particularly suitable for fine patterning using 254 to 193 nm far ultraviolet rays or excimer lasers, X-rays and electron beams among high energy rays. Further, when the above range is out of the upper limit and the lower limit, a desired pattern may not be obtained.

The resist material of the present invention is useful as a two-layer resist material because it has excellent oxygen plasma etching resistance by using a silicone polymer as a base resin.

That is, after forming a thick organic polymer layer as a lower resist on a substrate according to a conventional method, the resist solution of the present invention is spin-coated thereon. The upper resist layer of the present invention is patterned by the same method as described above, and then the lower resist is selectively etched by etching, so that the upper resist pattern can be formed in the lower layer.

A novolak resin-based positive resist can be used as the lower resist, and after coating on a substrate, hard baking is performed at 200 ° C. for 1 hour to prevent intermixing with a silicone-based resist. be able to.

[0211]

The positive resist material based on the high molecular silicone compound of the present invention is sensitive to high energy rays, and has excellent sensitivity and resolution. Useful. In particular, since the absorption at the exposure wavelength of the KrF excimer laser is small, a fine pattern perpendicular to the substrate can be easily formed. Further, because of its excellent oxygen plasma etching resistance, the two-layer resist obtained by applying the resist film of the present invention on the lower resist has a feature that a fine pattern can be formed with a high aspect ratio.

[0212]

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

[Synthesis Example 1] Synthesis of poly (p-hydroxybenzylsilsesquioxane) 1,200 mL of water was charged into a reactor, and p-methoxybenzyltrichlorosilane 487.
A mixed solution of 2 g (2.0 mol) and 600 mL of toluene was added dropwise over 2 hours to perform hydrolysis. Thereafter, the aqueous layer was removed by a liquid separation operation, and the organic layer was washed with water until the aqueous layer became neutral. 80 g of hexamethylsilazane to organic layer
Was added and refluxed for 5 hours. After cooling, toluene and unreacted hexamethylsilazane were distilled off by an evaporator, and then dissolved in 400 g of acetonitrile. 480 g of trimethylsilyl iodide was dropped into the solution at a temperature of 60 ° C. or lower, and the mixture was reacted at 60 ° C. for 10 hours. After completion of the reaction, hydrolysis was performed by adding 200 g of water,
Next, a polymer layer was obtained by decanting. After the solvent was removed by an evaporator, the polymer was dried under vacuum to obtain 330 g of poly (p-hydroxybenzylsilsesquioxane). The molecular weight of this polymer is determined by GPC
(Gel permeation chromatography), Mw = 3,500 in terms of polystyrene.
Met. In the analysis of ²⁹ Si-NMR, -6
Since no peak due to the SiOH group was observed at 2 ppm, it was confirmed that the SiOH group was sealed with a trimethylsilyl group.

[Synthesis Example 2] 160 g of the poly (p-hydroxybenzylsilsesquioxane) obtained in Synthesis Example 1 was added to 1,000 mL of dimethylformamide in a 2 L flask.
And a catalytic amount of p-toluenesulfonic acid was added thereto.
9.0 g and 6.0 g of triethylene glycol divinyl ether were added. After reacting for 1 hour, the mixture was neutralized with concentrated aqueous ammonia, and the neutralized reaction solution was added dropwise to 10 L of water to obtain a white solid. After filtering this, acetone 5
It was dissolved in 00 mL, added dropwise to 10 L of water, filtered, and dried under vacuum. From the ¹ H-NMR, it was confirmed from the ¹ H-NMR that the hydrogen atom of the hydroxyl group of poly (p-hydroxybenzylsilsesquioxane) was 20% ethoxyethylated and 3% was crosslinked (Polym. 1). ).

[Synthesis Example 3] A polymer was obtained in the same manner as in Synthesis Example 2, except that triethylene glycol divinyl ether was replaced with 5.0 g of 1,4-di (vinyl ether) cyclohexanone. The resulting polymer has ¹ H
-NMR confirmed that the hydrogen atom of the hydroxyl group of poly (p-hydroxybenzylsilsesquioxane) was ethoxyethylated by 20% and 2.5% was crosslinked (Po).
lym. 2).

[Synthesis Example 4] A polymer was obtained in the same manner as in Synthesis Example 2, except that 10.0 g of 1,4-di (vinyl ether) cyclohexanone was used instead of triethylene glycol divinyl ether. The resulting polymer is ¹
From H-NMR, it was confirmed that the hydrogen atom of the hydroxyl group of poly (p-hydroxybenzylsilsesquioxane) was ethoxyethylated by 19% and 4.8% was crosslinked (P
olym. 3).

[Synthesis Example 5] A polymer was obtained in the same manner as in Synthesis Example 2, except that ethyl vinyl ether was changed to 27.0 g of 1-ethoxypropene. From the ¹ H-NMR of the obtained polymer, it was confirmed that the hydrogen atom of the hydroxyl group of poly (p-hydroxybenzylsilsesquioxane) was ethoxypropylated by 20% and 2.9% was crosslinked (Polym). .4).

[Synthesis Example 6] A polymer was obtained in the same manner as in Synthesis Example 3, except that 35.0 g of 1-ethoxypropene was used in place of ethyl vinyl ether. From the ¹ H-NMR, the obtained polymer had 19.5% of hydrogen atoms of hydroxyl groups of poly (p-hydroxybenzylsilsesquioxane).
It was confirmed that ethoxypropylation was performed and 2.8% of the product was crosslinked (Polym. 5).

[Synthesis Example 7] A polymer was obtained in the same manner as in Synthesis Example 2, except that ethyl vinyl ether was replaced with 30.0 g of 2,3-dihydrofuran. The obtained polymer was found to have 19.0 hydrogen atoms of hydroxyl groups of poly (p-hydroxybenzylsilsesquioxane) by ¹ H-NMR.
% Tetrahydrofuranylated and 3% crosslinked (Polym. 6).

[Synthesis Example 8] 150 g of the partially crosslinked ethoxyethylated poly (p-hydroxybenzylsilsesquioxane) (Polym. 1) obtained in Synthesis Example 2 was dissolved in 1,200 mL of pyridine. While stirring with, 6.5 g of di-tert-butyl dicarbonate was added. 1
After reacting for an hour, the reaction solution was added dropwise to 10 L of water to obtain a white solid. After filtering this, acetone 500m
L, added dropwise to 10 L of water, filtered and dried in vacuo. The obtained polymer was analyzed by ¹ H-NMR for poly (p-
It was confirmed that 20% of the hydrogen atom of the hydroxyl group of hydroxybenzylsilsesquioxane) was ethoxyethylated, 3% was crosslinked, and the t-Boc conversion ratio was 3.0% (Polym. 7).

[Synthesis Examples 9 to 13] In the same manner as in Synthesis Example 8, Polym. 2 to 6 are converted to t-Boc and Pol
ym. 8-12 were obtained.

[Synthesis Example 14] A polymer was obtained in the same manner as in Synthesis Example 2, except that triethylene glycol divinyl ether was changed to 20.0 g of N, N'-bis (hydroxyethoxycarbonyl) phenylenediamine. The obtained polymer was analyzed by ¹ H-NMR for poly (p-
It was confirmed that the hydrogen atom of the hydroxyl group of hydroxybenzylsilsesquioxane) was ethoxyethylated at 18.0% and 1.9% was crosslinked.

According to a method similar to that of Synthesis Example 8, the obtained polymer was converted to t-Boc, 13 was obtained.

The structure of the obtained polymer is as shown in the following descriptive formula, and the substitution rate of the hydrogen atom of the hydroxyl group of each poly (p-hydroxybenzylsilsesquioxane) is shown in Table 1.
As shown in FIG.

In the following formula, R represents a group in which the following units are cross-linked to each other between molecules or within a molecule, and (R) represents a state in which a cross-linking group R is bonded.

[0226]

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[0227]

[Table 1]

[0228]

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[0229]

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[0230]

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[0231]

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[0232]

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[0233]

Embedded image

Examples and Comparative Examples Using the polymers (Polyms. 1 to 13) obtained in the above Synthesis Examples as base resins, acid generators represented by the following formulas (PAG. 1 to 7), (DRR.1-6) dissolution controlling agent represented by
The basic compound was dissolved in propylene glycol monoethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate / ethyl lactate (PGMEA / EL), and diethylene glycol monomethyl ether (DGLM) in the composition shown in Tables 2 to 4 to form a resist material. After the preparation, each composition was filtered through a 0.2 μm Teflon filter to prepare resist solutions.

For comparison, the following chemical formula (Poly) was used.
m. A resist solution was prepared in the same manner as described above using the polymer represented by (14, 15) as a base resin.

The obtained resist solution was spin-coated on a silicon wafer and applied to a thickness of 0.4 μm. Next, the silicon wafer was baked at 100 ° C. for 90 seconds using a hot plate. Use an excimer laser stepper (Nikon Corporation, NSR-2005EX)
8A, NA = 0.5) and exposed at 110 ° C. for 90
After baking for 2 seconds and developing with an aqueous solution of 2.38% tetramethylammonium hydroxide, a positive pattern could be obtained. The obtained resist pattern was evaluated as follows. The results are shown in Tables 2 to 4. Evaluation method : First, the sensitivity (Eth) was determined. Then 0.2
The exposure amount at which a 4 μm line and space was resolved at a ratio of 1: 1 was defined as the optimum exposure amount (Eop), and the minimum line width of the separated line and space at this exposure amount was defined as the resolution of the evaluation resist. The shape of the resolved resist pattern was observed using a scanning electron microscope. Also, 0.
The unevenness (edge roughness) of the 25 μm line and space was measured with a scanning electron microscope.

From the results of Tables 2 to 4, it was confirmed that the chemically amplified resist material of the present invention had a pattern with high resolution and no irregularities (small edge roughness).

[0238]

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[0239]

Embedded image

[0240]

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[0241]

Embedded image

[0242]

[Table 2]

[0243]

[Table 3] * TMMEA: Tris {(2-methoxymethoxy) ethyl} amine ** TMMEA: Tris [2-{(2-methoxyethoxy) methoxy} ethyl] amine

[0244]

[Table 4]

Example 36 OFPR800 (manufactured by Tokyo Ohka Co., Ltd.) was applied as a lower resist material to a silicon wafer to a thickness of 2.0 μm, and heated at 200 ° C. for 5 minutes.
Cured. The resist material used in Example 1 was applied on the lower resist film to a thickness of about 0.35 μm in the same manner as described above, and prebaked. Next, KrF excimer laser exposure and development were performed to form a pattern on the lower resist film. At this time, a pattern perpendicular to the lower resist film could be obtained, and the occurrence of footing was not recognized.

Thereafter, etching was performed with a parallel plate type sputter etching apparatus using oxygen gas as an etchant gas. The etching rate of the lower resist film is 150 nm /
min, whereas the present resist film has a thickness of 3 nm / min.
It was below. By etching for 15 minutes, the lower resist film that was not covered by the present resist film completely disappeared, and a two-layer resist pattern having a thickness of 2 μm or more was formed. The etching conditions are shown below. Gas flow rate: 50 sccm, gas pressure: 1.3 Pa, rf power: 50 W, dc bias: 450 V

────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] April 1, 1998

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claim 5

[Correction method] Change

[Correction contents]

Embedded image (Wherein, R ⁶ and R ⁷ represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms. Alternatively, R ⁶ and R ⁷ may form a ring, When forming a ring, R
^6, R ⁷ is a straight or branched alkylene group having 1 to 8 carbon atoms. R ⁸ is a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, and d is 0 or an integer of 1 to 5. A ′ is a c ″ -valent linear, branched or cyclic alkylene group having 1 to 20 carbon atoms, an alkyltriyl group, an alkyltetrayl group or an arylene group having 6 to 30 carbon atoms; The group may be intervening with a heteroatom,
Some of the hydrogen atoms bonded to the carbon atoms are hydroxyl groups,
It may be substituted by a carboxyl group, an acyl group or a fluorine atom. B is -CO-O-, -NHCO-O
-Or -NHCONH-. c '' is 2 to 4,
c ″ ′ is an integer of 1 to 3. )

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0020

[Correction method] Change

[Correction contents]

Claim 5: The crosslinking group having a C—O—C group represented by the general formula (4a) or (4b) is represented by the following general formula (4a ′) or (4b ′) High molecular silicone compound.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Toshinobu Ishihara 28-1 Nishifukushima, Oku-ku, Nakakushiro-gun, Niigata Pref. Shin-Etsu Chemical Co., Ltd.

Claims (10)

[Claims] 1. A high-molecular silicone compound having a phenolic hydroxyl group, wherein a part of hydrogen atoms of the phenolic hydroxyl group is substituted with at least one kind of acid labile group, further comprises a phenolic hydroxyl group. A high molecular weight silicone compound having a weight average molecular weight of 5,000 to 50,000, which is crosslinked with a crosslinking group having a C—O—C group within and / or between molecules. 2. A polymer silicone compound having a repeating unit represented by the following general formula (1), wherein a part of hydrogen atoms of a phenolic hydroxyl group is partially substituted by an acid labile group;
In addition, C- and C-forms within and / or between molecules obtained by reacting a part of the remaining phenolic hydroxyl groups with an alkenyl ether compound or a halogenated alkyl ether compound.
Cross-linked by a cross-linking group having an OC group, and the total amount of the acid labile group and the cross-linking group is more than 0 mol% on average and 80 mol% or less of all hydrogen atoms of the phenolic hydroxyl group. Item 7. The polymeric silicone compound according to Item 1. Embedded image (In the formula, Me represents a methyl group, x is an integer of 1 to 5, y is a positive number satisfying 0.001 ≦ y ≦ 0.05, z
Is an integer of 1 to 3. ) 3. An intramolecular and / or intramolecular compound obtained by reacting a phenolic hydroxyl group represented by R with an alkenyl ether compound or a halogenated alkyl ether compound of a polymer silicone compound having a repeating unit represented by the following general formula (2): 3. The high molecular silicone compound according to claim 2, which is crosslinked by a crosslinking group having a C--O--C group between molecules. Embedded image (Wherein Me is a methyl group, R is a hydroxyl group or an OR ¹ group, at least one is a hydroxyl group. R ¹ is an acid labile group, m is 0 or an integer of 1 to 5, n Is an integer of 1 to 5, and is a number satisfying m + n ≦ 5, and x is 1 to 5.
5, y is a positive number satisfying 0.001 ≦ y ≦ 0.05, and z is an integer of 1 to 3. p and q are positive numbers and satisfy p + q = 1. ) 4. A high molecular silicone compound having a repeating unit represented by the following general formula (3), wherein a hydrogen atom of a phenolic hydroxyl group represented by R is removed and its oxygen atom is converted to the following general formula (4a) or (4b) The polymer silicone compound according to claim 3, which is crosslinked intra- and / or intermolecularly by a cross-linking group having a C-O-C group represented by the formula: Embedded image (Wherein Me is a methyl group, R is a hydroxyl group or an OR ¹ group, at least one is a hydroxyl group, R ¹ is an acid labile group, R ² and R ³ are a hydrogen atom or a carbon atom 1-8 linear, branched or cyclic alkyl group, R ⁴ represents a may monovalent which may have a hetero atom of a hydrocarbon group having 1 to 18 carbon atoms, R ² and R ³ , R ² and R ⁴ , and R ³ and R ⁴ may form a ring, and when forming a ring, R ² , R ³ , R
⁴ represents a linear or branched alkylene group having 1 to 18 carbon atoms. R ⁵ is a tertiary alkyl group, each alkyl moiety has trialkylsilyl group having 1 to 6 carbon atoms having 4 to 20 carbon atoms, or oxoalkyl groups of 4 to 20 carbon atoms -
And a group represented by CR ² R ³ OR ⁴ . p1 and p2 are positive numbers, q1 and q2 are 0 or positive numbers, and 0 <p1 / (p1
+ P2 + q1 + q2) ≦ 0.8, 0 ≦ q1 / (p1 + p
2 + q1 + q2) ≦ 0.8, 0 ≦ q2 / (p1 + p2 +
q1 + q2) ≦ 0.8, which satisfies p1 + p2 + q1 + q2 = 1, but q1 and q2 do not become 0 at the same time. a is 0 or an integer of 1 to 6. m, n, x,
y and z each have the same meaning as described above. ) (Wherein, R ⁶ and R ⁷ represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms. Alternatively, R ⁶ and R ⁷ may form a ring, When a ring is formed, R ⁶ and R ^{7 each} represent a linear or branched alkylene group having 1 to ⁸ carbon atoms, and R ⁸ represents a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms. And d is 0 or an integer of 1 to 10. A represents a c-valent aliphatic or alicyclic saturated hydrocarbon group having 1 to 50 carbon atoms, an aromatic hydrocarbon group or a heterocyclic group, May have a heteroatom interposed,
Some of the hydrogen atoms bonded to the carbon atoms are hydroxyl groups,
It may be substituted by a carboxyl group, an acyl group or a fluorine atom. B is -CO-O-, -NHCO-O
-Or -NHCONH-. c is 2 to 8, c 'is 1
-7. ) 5. The crosslinking group having a C—O—C group represented by the general formula (4a) or (4b) is represented by the following general formula (4a ′)
Or the chemically amplified positive resist material according to claim 4, which is represented by (4b '). Embedded image (Wherein, R ⁶ and R ⁷ represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms. Alternatively, R ⁶ and R ⁷ may form a ring, When a ring is formed, R ⁶ and R ^{7 each} represent a linear or branched alkylene group having 1 to ⁸ carbon atoms, and R ⁸ represents a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms. And d is an integer of 0 or 1 to 5. A ′ is a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms, an alkyltriyl group or an alkyltetrayl group having a c ″ valency. Or an arylene group having 6 to 30 carbon atoms, and these groups may have a hetero atom interposed;
Some of the hydrogen atoms bonded to the carbon atoms are hydroxyl groups,
It may be substituted by a carboxyl group, an acyl group or a fluorine atom. B is -CO-O-, -NHCO-O
-Or -NHCONH-. c '' is 2 to 4,
c ″ ′ is an integer of 1 to 3. ) 6. An organic solvent according to claim 1, wherein (A) is an organic solvent and (B) is a base resin.
4. A chemically amplified positive resist material comprising the polymer silicone compound (C): an acid generator according to the above item (1). 7. The chemically amplified positive resist material according to claim 6, further comprising (D) a dissolution controlling agent. 8. The chemically amplified positive resist composition according to claim 6, further comprising (E) a basic compound as an additive. 9. Further, as a base resin different from the component (F) :( B), one hydrogen atom of a phenolic hydroxyl group of a high molecular silicone compound having a repeating unit represented by the following general formula (1) may be used. Alternatively, a high molecular weight silicone compound having a weight average molecular weight of 3,000 to 300,000 partially substituted by two or more kinds of acid labile groups at an average ratio of 0 mol% to 80 mol% as a whole is compounded. The chemically amplified positive resist material according to claim 6. Embedded image (In the formula, Me represents a methyl group, x is an integer of 1 to 5, y is a positive number satisfying 0.001 ≦ y ≦ 0.05, z
Is an integer of 1 to 3. ) 10. A step of (i) applying the chemically amplified positive resist material according to any one of claims 6 to 9 onto a substrate, and (ii) subsequently applying a wavelength through a photomask after a heat treatment. A pattern forming method, comprising: a step of exposing with a high energy beam or an electron beam of 300 nm or less; and (iii) a step of performing a heat treatment as necessary and then developing with a developer.