JP3533951B2 - Polymeric silicone compound, resist material and pattern forming method - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polymer silicone compound suitable as a base resin for a resist material used for microfabrication in the manufacturing process of semiconductor devices and the like, and deep ultraviolet rays, KrF excimer laser light (248 nm),
ArF excimer laser light (193 nm), electron beam, X
The present invention relates to a resist material suitable for using a high energy ray such as a ray as an exposure light source, and a pattern forming method.

[0002]

2. Description of the Related Art In recent years,
Along with the high integration and high speed of LSIs, the miniaturization of pattern rules is required, and in the photoexposure currently used as a general-purpose technique, the essential resolution limit derived from the wavelength of the light source is approached. It's starting. In photoexposure using a g-line (436 nm) or an i-line (365 nm) as a light source, the pattern rule of about 0.5 μm is the limit, and the integration degree of an LSI manufactured using this is 16 Mbit D
Up to RAM equivalent. However, the trial manufacture of the LSI has already reached this stage, and the development of further miniaturization technology is urgently needed.

As one of the means for miniaturizing the pattern, there is a method of shortening the wavelength of the exposure light used for forming the resist pattern, which is 256 M bits (processing dimension: 0.
In the mass production process of DRAM (Dynamic Random Access Memory) (25 μm or less), the use of a short wavelength KrF excimer laser (248 nm) as an exposure light source is currently actively considered as an exposure light source. . However, a DRA with an integration degree of 1G or more that requires finer processing technology (processing dimension is 0.2 μm or less)
The manufacture of M requires shorter wavelength light sources, especially A
Photography using an rF excimer laser (193 nm) has recently been studied.

Here, in the case of lithography using short wavelength light of 220 nm or less represented by ArF excimer laser, a photoresist is required to have new characteristics that cannot be satisfied by conventional materials in order to form a fine pattern. . Therefore, Ito et al. Have proposed a chemically amplified positive resist material in which an acid generator of an onium salt is added to a resin called PBOCST in which a hydroxyl group of polyhydroxystyrene is protected by a tert-butoxycarbonyloxy group (t-Boc group). Since the proposal, various high-sensitivity and high-resolution resist materials have been developed. However, although all of these resist materials have high sensitivity and high resolution, it is difficult to form a fine pattern with a high aspect ratio in view of the mechanical strength of the pattern obtained from them. .

Further, the above polyhydroxystyrene is used as a base resin, and deep ultraviolet rays, electron beams and X-rays are used.
Many resist materials having sensitivity to rays have been proposed in the past. However, in order to form a pattern with a high aspect ratio on a stepped substrate, the two-layer resist method is excellent, whereas all the above resist materials are based on the single-layer resist method, and the problem of the substrate step still remains. At present, there are problems of light reflection from the substrate and problems of forming a pattern with a high aspect ratio, which makes it difficult to put it into practical use.

On the other hand, it has been conventionally known that a two-layer resist method is excellent for forming a pattern having a high aspect ratio on a stepped substrate. Further, a two-layer resist film is used as a general alkaline developing solution. It is known that a high molecular silicone compound having a hydrophilic group such as a hydroxy group or a carboxyl group is required for development with. However, in the case of silanol in which a hydroxyl group is directly bonded to a high molecular weight silicone compound, a cross-linking reaction is caused by an acid, so that it is difficult to apply it to a chemically amplified positive resist material.

In recent years, as a silicone-based resist material for solving these problems, polyhydroxybenzylsilsesquioxane, which is a stable alkali-soluble silicone polymer, is prepared by partially protecting a phenolic hydroxyl group with a t-Boc group. A silicone-based chemically amplified positive resist material which is used as a resin and is combined with an acid generator has been proposed (JP-A-7-118651, S).
PIE vol. 1952 (1993) 377).

However, the polymers used in these silicone resist materials have an aromatic ring,
At wavelengths of 220 nm and below, the light absorption by the aromatic ring is extremely strong.
It cannot be applied to photography using short-wavelength light of 0 nm or less (that is, most of the exposure light is absorbed by the surface of the resist, and the exposure does not reach the substrate, so a fine resist pattern cannot be formed [Sasako et al. ArF Excimer Laser Lithography (3) -Resist Evaluation- ", 3rd
Proceedings of the 5th Joint Lecture Meeting of the Japan Society of Applied Physics, 1P-K
4 (1989)]).

As an example of a silicone-based resist material which does not have a phenyl group as a base resin, Japanese Patent Application Laid-Open No. Hei 5-
As disclosed in Japanese Patent No. 323611, this base polymer protects all hydrophilic groups such as carboxyl group and hydroxy group necessary for enabling alkali development, so that the exposed portion is dissolved in a developing solution. To do so, many protecting groups must be cleaved off. Therefore, the amount of the acid generator to be added increases and the sensitivity deteriorates. In addition, there is a high possibility of causing a change in film thickness, stress in the film, or generation of bubbles in the film when many protective groups are decomposed, and it does not provide a resist material with high sensitivity and suitable for fine processing. It was a thing.

The present invention has been made in view of the above circumstances, and it can be suitably used as a material for a two-layer resist method which has high sensitivity and high resolution and is particularly suitable for forming a pattern having a high aspect ratio. In addition, a novel polymer silicone compound useful as a base polymer of a resist material capable of forming a pattern having excellent heat resistance, a resist material containing the compound as a base polymer, and a pattern forming method are provided. To do.

[0011]

Means for Solving the Problems and Modes for Carrying Out the Invention As a result of intensive studies to achieve the above object, the present inventors have found that a polymeric silicone having a repeating unit represented by the following general formula (1). In the compound or the polymeric silicone compound, a part or all of the hydrogen atoms of the carboxyl group or the carboxyl group and the hydroxyl group are substituted with one or more acid labile groups (that is, the polymer of formula (1) The hydrogen atom of the carboxyl group or the carboxyl group and the hydroxyl group of the silicone compound is substituted by the acid labile group at a ratio of 0 to 100 mol%), and the weight average molecular weight is 1,000.
˜50,000 aromatic ring-free polymeric silicone compound, positive resist material containing an acid generator added thereto,
Alternatively, a negative resist material added with a compound capable of being crosslinked by the action of an acid, particularly a resist material prepared by adding a dissolution control agent in addition to an acid generator, or a resist material prepared by further mixing a basic compound therein is used for resist dissolution. In order to increase the contrast, in particular, to increase the dissolution rate after exposure, a resist material containing a compound having a group represented by ≡C-COOH in the molecule improves the PED stability of the resist and improves the PED stability of the resist. By improving the edge roughness of the composition, and by compounding an acetylene alcohol derivative, the coating property and storage stability are improved. Therefore, the silicone-based resist material according to the present invention has high transparency, high resolution, and exposure margin. It is highly effective as a resist material for VLSI, which is excellent in precision and process adaptability, has high practicality, and is advantageous for precise microfabrication. And finding that there were able to complete the present invention.

That is, the present invention provides the following polymeric silicone compound, a resist material containing the same, and a pattern forming method.

1. A polymer silicone compound comprising a repeating unit represented by the following general formula (1) and having a weight average molecular weight of 1,000 to 50,000.

[0014]

[Chemical 12] [In the formula, Z is a divalent to hexavalent non-aromatic monocyclic or polycyclic hydrocarbon group having 5 to 12 carbon atoms or a bridged cyclic hydrocarbon group, and Z ′ is a divalent to hexavalent one. A linear or branched hydrocarbon group having 1 to 20 carbon atoms, or a non-aromatic monocyclic or polycyclic hydrocarbon group having 3 to 20 carbon atoms or a bridged cyclic hydrocarbon group, These groups may have a nitrogen atom, an oxygen atom or a sulfur atom interposed between carbon-carbon bonds,
A hydrogen atom on a carbon atom is a halogen atom, an alkoxy group,
It may be substituted with a nitro group, a cyano group or an acetyl group, and the methylene group in the carbon skeleton may be substituted with a carbonyl group.

X, y and z are determined according to the valences of Z and Z '.
Each represents an integer of 1 to 5.

R ¹ is a group represented by the following general formula (2a) or (2b), R ² is a linear, branched or cyclic C 1-8 unsubstituted or substituted alkyl or alkenyl group, Alternatively, a non-aromatic monovalent polycyclic hydrocarbon group having 5 to 12 carbon atoms or a bridged cyclic hydrocarbon group is shown.

[0017]

[Chemical 13] (In the formula, R represents a hydrogen atom, a hydroxyl group or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and R'is a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms. In these alkyl groups and alkylene groups, an oxygen atom may be present in the carbon-carbon bond, or a part of the carbon-bonded hydrogen atoms may be substituted with a hydroxyl group. 'May form a ring with each other, and in the case of forming a ring, R and R'each have 1 to 8 carbon atoms.
Represents a linear or branched alkylene group. ) Expression (1)
, P1 , p2, p4 are positive numbers, p3 is 0 or a positive number, and p1 + p2 + p3 + p4 = 1, and 0 <p1 / (p1 + p2 + p3 + p4) ≦ 0.9 0 <p2 / (p1 + p2 + p3 + p4) ≦ 0.8 0 ≦ It is a number satisfying p3 / (p1 + p2 + p3 + p4) ≦ 0.7 0 <p4 / (p1 + p2 + p3 + p4) ≦ 0.9 . ]

(2) A part or all of the hydrogen atoms of the carboxyl group or the carboxyl group and the hydroxyl group of the polymer silicone compound comprising the repeating unit represented by the general formula (1) according to claim 1 is 1.
A high molecular weight silicone compound having a weight average molecular weight of 1,000 to 50,000, which is substituted with one or two or more acid labile groups.

3. A polymer silicone compound represented by the above general formula (1), wherein a part of hydrogen atoms of a carboxyl group or a carboxyl group and a hydroxyl group is partially substituted by one or more acid labile groups. The remaining hydrogen atoms of the carboxyl group and / or the hydroxyl group exceeds 0 mol% of the hydrogen atoms of the carboxyl group and the hydroxyl group of the whole polymer silicone compound of the formula (1) 50
Intramolecularly and / or intermolecularly crosslinked by substituting with a group having a C—O—C group represented by the following general formula (3a) or (3b) at a ratio of not more than mol%:
The described polymeric silicone compound.

[0020]

[Chemical 14] (In the formula, R ³ and R ⁴ represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms. Alternatively, R ³ and R ⁴ may form a ring, When forming a ring, R ³ and R ^{4 each} represent a linear or branched alkylene group having 1 to 8 carbon atoms, and R ⁵ represents a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms. Group, 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, The group of may have a heteroatom interposed,
Further, a part of hydrogen atoms bonded to the carbon atom is a hydroxyl group,
It may be substituted with a carboxyl group, an acyl group or a fluorine atom. B is -CO-O-, -NHCO-O
-Or-NHCONH- is shown. c is 2-8, c'is 1
Is an integer of ~ 7. )

Claim 4: The cross-linking group having a C-O-C group represented by the general formula (3a) or (3b) is represented by the following general formula (3a ''') or (3).
The polymer silicone compound according to claim 3, which is represented by b ′ ″).

[0022]

[Chemical 15] (In the formula, R ³ and R ⁴ represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms. Alternatively, R ³ and R ⁴ may form a ring, When forming a ring, R ³ and R ^{4 each} represent a linear or branched alkylene group having 1 to 8 carbon atoms, and R ⁵ represents a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms. Group, 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. Alternatively, it represents an arylene group having 6 to 30 carbon atoms, and these groups may have a heteroatom interposed therebetween,
Further, a part of hydrogen atoms bonded to the carbon atom is a hydroxyl group,
It may be substituted with a carboxyl group, an acyl group or a fluorine atom. B is -CO-O-, -NHCO-O
-Or-NHCONH- is shown. c '' is 2-4,
c ″ ′ is an integer of 1 to 3. )

Claim 5: The acid labile group is a group represented by the following general formula (4), a group represented by the following general formula (5), a tertiary alkyl group having 4 to 20 carbon atoms, or each alkyl group. The polymer silicone compound according to claim 2, 3 or 4, which is one or more groups selected from a trialkylsilyl group having 1 to 6 carbon atoms and an oxoalkyl group having 4 to 20 carbon atoms.

[0024]

[Chemical 16] (R ⁶ and R ⁷ represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, and R ⁸ represents 1 carbon atom.
~ 18 a monovalent hydrocarbon group which may have a hetero atom, R ⁶ and R ⁷ , R ⁶ and R ⁸ or R ⁷ and R ⁸ may form a ring, When formed, R ⁶ , R ⁷ and R ⁸ each represent a linear or branched alkylene group having 1 to 18 carbon atoms. R ⁹ is a tertiary alkyl group having 4 to 20 carbon atoms, a trialkylsilyl group having 1 to 6 carbon atoms in each alkyl group,
An oxoalkyl group having 4 to 20 carbon atoms or a group represented by the above general formula (4) is shown. a is an integer of 0-6. )

(6) A resist material containing the high molecular silicone compound according to any one of (1) to (5).

Claim 7: (A) Organic solvent (B) A polymeric silicone compound having a repeating unit represented by the following general formula (1) or a carboxyl group of the polymeric silicone compound or a hydrogen atom of a carboxyl group and a hydroxyl group. A weight average molecular weight of 1,000 to 5 which is partially or wholly substituted by one or more acid labile groups.
10,000 high molecular silicone compounds,

[0027]

[Chemical 17] [In the formula, Z is a divalent to hexavalent non-aromatic monocyclic or polycyclic hydrocarbon group having 5 to 12 carbon atoms or a bridged cyclic hydrocarbon group, and Z ′ is a divalent to hexavalent one. A linear or branched hydrocarbon group having 1 to 20 carbon atoms, or a non-aromatic monocyclic or polycyclic hydrocarbon group having 3 to 20 carbon atoms or a bridged cyclic hydrocarbon group, These groups may have a nitrogen atom, an oxygen atom or a sulfur atom interposed between carbon-carbon bonds,
A hydrogen atom on a carbon atom is a halogen atom, an alkoxy group,
It may be substituted with a nitro group, a cyano group or an acetyl group, and the methylene group in the carbon skeleton may be substituted with a carbonyl group.

X, y and z are determined according to the valences of Z and Z '.
Each represents an integer of 1 to 5. R ¹ is represented by the following general formula (2
a) or (2b), R ² is a linear, branched or cyclic C 1-8 unsubstituted or substituted alkyl or alkenyl group, or C 5-12 non-aromatic A monovalent polycyclic hydrocarbon group or a bridged cyclic hydrocarbon group of the system is shown.

[0029]

[Chemical 18] (In the formula, R represents a hydrogen atom, a hydroxyl group or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and R'is a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms. In these alkyl groups and alkylene groups, an oxygen atom may be present in the carbon-carbon bond, or a part of the carbon-bonded hydrogen atoms may be substituted with a hydroxyl group. 'May form a ring with each other, and in the case of forming a ring, R and R'each have 1 to 8 carbon atoms.
Represents a linear or branched alkylene group. ) Expression (1)
, P1 , p2, p4 are positive numbers, p3 is 0 or a positive number, and p1 + p2 + p3 + p4 = 1, and 0 <p1 / (p1 + p2 + p3 + p4) ≦ 0.9 0 <p2 / (p1 + p2 + p3 + p4) ≦ 0.8 0 ≦ It is a number satisfying p3 / (p1 + p2 + p3 + p4) ≦ 0.7 0 <p4 / (p1 + p2 + p3 + p4) ≦ 0.9 . Further, the above general formula (1) in which a part of hydrogen atoms of a carboxyl group or a carboxyl group and a hydroxyl group is partially substituted with one or more kinds of acid labile groups.
In the proportion of more than 0 mol% and not more than 50 mol% of the total hydrogen atoms of the remaining carboxyl groups and / or hydroxyl groups of the polymer silicone compound represented by the following general formula (3a) or (3
It may be crosslinked intramolecularly and / or intermolecularly by substituting with a group having a C—O—C group shown in b).

[0030]

[Chemical 19] (In the formula, R ³ and R ⁴ represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms. Alternatively, R ³ and R ⁴ may form a ring, R when forming a ring
³ and R ^{4 each} represent a linear or branched alkylene group having 1 to 8 carbon atoms. R ⁵ is 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, and these groups may have a heteroatom interposed therebetween,
Further, a part of hydrogen atoms bonded to the carbon atom is a hydroxyl group,
It may be substituted with a carboxyl group, an acyl group or a fluorine atom. B is -CO-O-, -NHCO-O
-Or-NHCONH- is shown. c is 2-8, c'is 1
Is an integer of ~ 7. )] (C) A resist material containing an acid generator.

Claim 8: The acid labile group is a group represented by the general formula (4), a group represented by the general formula (5), a tertiary alkyl group having 4 to 20 carbon atoms, or each alkyl group. The resist material according to claim 7, which is one or more groups selected from a trialkylsilyl group having 1 to 6 carbon atoms and an oxoalkyl group having 4 to 20 carbon atoms. Claim 9: The resist material according to claim 7 or 8, further comprising (D) a dissolution control agent.

Item 10: The resist material according to item 7, 8 or 9, further comprising (E) a basic compound.

(11) The resist material according to any one of (7) to (10), further comprising (F): a compound having a group represented by ≡C-COOH in the molecule.

Item 12: The resist material according to any one of items 7 to 11, further comprising (G): an acetylene alcohol derivative.

(A) Organic solvent (B) Polymeric silicone compound having a repeating unit represented by the following general formula (1), or carboxyl group of the polymeric silicone compound or one of hydrogen atoms of carboxyl group and hydroxyl group A weight average molecular weight of 1,000 to 50,000, in which one part or two or more kinds of acid labile groups are substituted.
0 polymer silicone compound,

[0036]

[Chemical 20] [In the formula, Z is a divalent to hexavalent non-aromatic monocyclic or polycyclic hydrocarbon group having 5 to 12 carbon atoms or a bridged cyclic hydrocarbon group, and Z ′ is a divalent to hexavalent one. A linear or branched hydrocarbon group having 1 to 20 carbon atoms, or a non-aromatic monocyclic or polycyclic hydrocarbon group having 3 to 20 carbon atoms or a bridged cyclic hydrocarbon group, These groups may have a nitrogen atom, an oxygen atom or a sulfur atom interposed between carbon-carbon bonds,
A hydrogen atom on a carbon atom is a halogen atom, an alkoxy group,
It may be substituted with a nitro group, a cyano group or an acetyl group, and the methylene group in the carbon skeleton may be substituted with a carbonyl group.

X, y and z depend on the valences of Z and Z '.
Each represents an integer of 1 to 5. R ¹ is represented by the following general formula (2
a) or (2b), R ² is a linear, branched or cyclic C 1-8 unsubstituted or substituted alkyl or alkenyl group, or C 5-12 non-aromatic A monovalent polycyclic hydrocarbon group or a bridged cyclic hydrocarbon group of the system is shown.

[0038]

[Chemical 21] (In the formula, R represents a hydrogen atom, a hydroxyl group or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and R'is a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms. In these alkyl groups and alkylene groups, an oxygen atom may be present in the carbon-carbon bond, or a part of the carbon-bonded hydrogen atoms may be substituted with a hydroxyl group. 'May form a ring with each other, and in the case of forming a ring, R and R'each have 1 to 8 carbon atoms.
Represents a linear or branched alkylene group. ) Expression (1)
, P1 , p2, p4 are positive numbers, p3 is 0 or a positive number, and p1 + p2 + p3 + p4 = 1, and 0 <p1 / (p1 + p2 + p3 + p4) ≦ 0.9 0 <p2 / (p1 + p2 + p3 + p4) ≦ 0.8 0 ≦ It is a number satisfying p3 / (p1 + p2 + p3 + p4) ≦ 0.7 0 <p4 / (p1 + p2 + p3 + p4) ≦ 0.9 . Further, the above general formula (1) in which a part of hydrogen atoms of a carboxyl group or a carboxyl group and a hydroxyl group is partially substituted with one or more kinds of acid labile groups.
In the proportion of more than 0 mol% and not more than 50 mol% of the total hydrogen atoms of the remaining carboxyl groups and / or hydroxyl groups of the polymer silicone compound represented by the following general formula (3a) or (3
It may be crosslinked intramolecularly and / or intermolecularly by substituting with a group having a C—O—C group shown in b).

[0039]

[Chemical formula 22] (In the formula, R ³ and R ⁴ represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms. Alternatively, R ³ and R ⁴ may form a ring, R when forming a ring
³ and R ^{4 each} represent a linear or branched alkylene group having 1 to 8 carbon atoms. R ⁵ is 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, and these groups may have a heteroatom interposed therebetween,
Further, a part of hydrogen atoms bonded to the carbon atom is a hydroxyl group,
It may be substituted with a carboxyl group, an acyl group or a fluorine atom. B is -CO-O-, -NHCO-O
-Or-NHCONH- is shown. c is 2-8, c'is 1
Is an integer of ~ 7. )] A resist material comprising (C) an acid generator and (H) a compound which is crosslinked by the action of an acid.

Claim 14: The acid labile group is a group represented by the general formula (4), a group represented by the general formula (5), a tertiary alkyl group having 4 to 20 carbon atoms, or each alkyl group. The resist material according to claim 13, which is one or more groups selected from a trialkylsilyl group having 1 to 6 carbon atoms and an oxoalkyl group having 4 to 20 carbon atoms. Claim 15: (i) a step of applying the resist material according to any one of claims 6 to 14 on a substrate, and (ii) a high energy ray having a wavelength of 300 nm or less through a photomask after the heat treatment. Alternatively, a pattern forming method comprising: a step of exposing with an electron beam; and (iii) a step of performing a heat treatment as necessary and then developing with a developing solution.

That is, the inventors of the present invention disclosed in Japanese Patent Laid-Open No. 6-1186.
Other than the polymer silicone compound having a phenyl group as described in JP-A-51, it provides high transmittance for light in the far-ultraviolet region and does not protect all alkali-soluble groups with acid labile groups. We investigated and searched for a polymer that can be protected from scratches and give high resolution. On the other hand, examples of the polymer silicone compound having no phenyl group include polymer silicone compounds having an ethylcarboxyl group as described in JP-A-5-323611. By reacting the possessed polysiloxane with an unsaturated carboxylic acid such as methacrylic acid, an addition reaction occurs exclusively at the α-position of the unsaturated carboxylic acid, and it is difficult to obtain a polymer silicone compound as exemplified. In addition, performing a hydrosilylation reaction into a polymer compound is
Quantitatively difficult, stable supply of high molecular silicone compound becomes difficult, and further quality control of resist becomes difficult.

In contrast to such a polymer compound, a resist using a polymer silicone compound in which an acid labile group is introduced into a part of the carboxyl group of the polymer silicone compound having no aromatic ring as described above. The material is 220 nm
The inventors of the present invention have completed the present invention by discovering that they have high transparency to the following short-wavelength light and can form a pattern with these exposure lights.

Further, a polymeric silicone compound crosslinked intramolecularly and / or intermolecularly with a crosslinking group having a C--O--C group obtained by the reaction of a carboxyl group with an alkenyl ether compound and / or a halogenated alkyl ether compound. The resist material using is effective in inhibiting dissolution with a small amount of crosslinking, and the heat resistance is improved by increasing the molecular weight due to crosslinking. Moreover, since the cross-linking group is eliminated after the exposure than before the exposure, the molecular weight of the polymer is reduced, so that the dissolution contrast of the resist film can be increased, resulting in high sensitivity and high resolution. .
In addition, since there are few problems with the surface insoluble layer and the occurrence of skirting, it is possible to arbitrarily control the pattern dimension and pattern shape depending on the composition, and it becomes a resist material with excellent process adaptability. Based on this finding, the present invention has been completed.

The present invention will be described in more detail below. The novel polymeric silicone compound of the present invention comprises a polymeric silicone compound having a repeating unit represented by the following general formula (1), if necessary, an acid labile group and / or Alternatively, a crosslinking group is introduced.

[0045]

[Chemical formula 23]

Here, Z is a divalent to hexavalent carbon number 5 to 12
Are non-aromatic monocyclic or polycyclic hydrocarbon groups or bridged cyclic hydrocarbon groups, and specific hydrocarbon groups include, but are not limited to, the following hydrocarbon groups. That is,
As the hydrocarbon group, a cyclopentanediyl group, a cyclohexanediyl group, a cycloheptanediyl group, a cyclopentanetriyl group, a cyclohexanetriyl group, a cycloheptanetriyl group, a cyclohexanetetrayl group,
Cyclohexanepentyl group, cyclohexanehexayl group, cyclooctanediyl group, cyclononanediyl group, cyclodecanediyl group, cyclooctanetriyl group, cyclononanetriyl group, cyclodecanetriyl group, norbornanediyl group, isobornanediyl group Group, norbornanetriyl group, isobornanetriyl group, adamantanediyl group, tricyclo [5,2,1,0 ^2,6 ]
Decanediyl group, adamantanetriyl group, tricyclo [5,2,1,0 ^2,6 ] decanetriyl group, tricyclo [5,2,1,0 ^2,6 ] decane methylenediyl group, tricyclo [5,2,1, 0 ^2,6] decane-methylene tri-yl group, tetracyclo [4,4,0,1 ^2,5, 1 ^7,10] dodecanediyl group, tetracyclo [4,4,0,1 ^2,5, 1
^2,10 ] dodecanetriyl group and the like.

Z'is a divalent to hexavalent straight-chain or branched hydrocarbon group having 1 to 20 carbon atoms or a non-aromatic monocyclic or polycyclic hydrocarbon group having 3 to 20 carbon atoms. Or a bridged cyclic hydrocarbon group, and these groups may have a nitrogen atom, an oxygen atom or a sulfur atom interposed between carbon-carbon bonds, and the hydrogen atom on the carbon atom is a halogen atom or an alkoxy group. , A nitro group, a cyano group or an acetyl group may be substituted, and the methylene group in the carbon skeleton may be substituted with a carbonyl group.

Here, the divalent to hexavalent straight-chain or branched hydrocarbon group having 1 to 20 carbon atoms is an alkyl group or an alkenyl group, and the valence number M thereof depends on the valence number M.
Examples thereof include groups in which carbon-bonded hydrogen atoms are eliminated by the number obtained by subtracting 1 (the number of M-1). For example, in the case of divalence, examples include an alkylene group and an alkenylene group. However, in the case of a hydrocarbon group having 1 carbon atom, the maximum valence is 4
Also, in the case of an unsaturated hydrocarbon group having 2 carbon atoms, the maximum valence is 4.

When a nitrogen atom is present between carbon-carbon bonds, it can be present as --C--NH--C--, and when it is an oxygen atom or a sulfur atom, --C--O--C is respectively present.
-,-C-S-C-

Further, examples of the halogen atom which replaces the hydrogen atom on the carbon atom include F, Cl and Br.
The alkoxy group is preferably an alkoxy group having 1 to 6 carbon atoms such as methoxy, ethoxy, propoxy, isopropoxy, n-butyloxy, isobutyloxy, tert-butyloxy. And a methylene group in the carbon skeleton is replaced by a carbonyl group, for example, -CH ₂ - CH ₂ -CH ₂ - is -CH ₂ - refers become possible _{- C (= O) -CH 2} .

Specifically, as Z ', a methylene group, an ethylene group, a propanediyl group, a butanediyl group, a pentanediyl group, a hexanediyl group, a heptanediyl group, an octanediyl group, a nonanediyl group, a decanediyl group, an isopropanediyl group, Isobutanediyl group, sec-butanediyl group, tert-butanetriyl group, isopentanediyl group, neopentanetriyl group, vinyl group, allyl group, propenediyl group, butenediyl group, hexenediyl group, cyclopentanediyl group, cyclopentenediyl group, cyclohexanediyl Group, cyclohexenediyl group, cycloheptanediyl group, cyclopentanetriyl group, cyclohexanetriyl group, cycloheptanetriyl group, cyclohexanetetrayl group, cyclohexanepentyl group, cyclo Rohexanehexayl group, cyclooctanediyl group, cyclononanediyl group, cyclodecanediyl group, cyclooctanetriyl group, cyclononanetriyl group, cyclodecanetriyl group, cyclopentanemethylenediyl group, cyclohexanemethylenediyl group, cyclohexane -4,4-dimethylenetriyl group, norbornanediyl group, isobornanediyl group, norbornanetriyl group, isobornanetriyl group, norbornane-
5,5-dimethylenetriyl group, adamantanediyl group, adamantanemethylenediyl group, adamantanetriyl group, adamantanemethylenetriyl group, tricyclo [5,2,1,0 ^2,6 ] decanediyl group, tricyclo [5,5] 2,1,0 ^2,6 ] decanetriyl group, tricyclo [5,2,1,0 ^2,6 ] decane methylenediyl group, tricyclo [5,2,1,0 ^2,6 ] decane methylenetriyl group, tetracyclo [4,4,0,1 ^2,5, 1 ^7,10] dodecanediyl group, tetracyclo [4,4,0,1 ^2,5, 1
^7,10 ] dodecanetriyl group and the like.

X, y and z depend on the valences of Z and Z '.
Each represents an integer of 1 to 5, preferably 1 each.
To 3, and more preferably 1 or 2.

R ¹ is a group represented by the following general formula (2a) or (2b).

[0054]

[Chemical formula 24] (In the formula, R represents a hydrogen atom, a hydroxyl group or a linear or branched alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and R ′ represents 1 carbon atom. ~ 2
0, preferably 1 to 10, and more preferably 1 to 6 linear, branched or cyclic alkylene groups are shown, and these alkyl groups and alkylene groups may have carbon atoms bonded to each other through oxygen atoms. Well, a part of the carbon-bonded hydrogen atoms may be replaced with a hydroxyl group. Further, R and R ′ may form a ring with each other, and in the case of forming a ring, R and R ′ each represent a linear or branched alkylene group having 1 to 8 carbon atoms. )

Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, octyl group,
A decyl group, a myristyl group and the like can be mentioned, and as the alkylene group, a methylene group, an ethylene group, a propylene group,
Examples thereof include an isopropylene group, a butylene group, an isobutylene group, a hexylene group, a cyclohexylene group, and an octylene group.

Specific examples of the groups of the above formulas (2a) and (2b) include, but are not limited to, the following groups.

[0057]

[Chemical 25]

In the above formula (1), R ² is a linear, branched or cyclic C 1-8 unsubstituted or substituted alkyl or alkenyl group, or C 5-12.
Is a non-aromatic monovalent polycyclic hydrocarbon group or a bridged cyclic hydrocarbon group.

Here, the straight-chain, branched or cyclic unsubstituted alkyl group or alkenyl group having 1 to 8 carbon atoms includes
Methyl group, ethyl group, propyl group, isopropyl group, n
-Butyl group, isobutyl group, tert-butyl group, cyclohexyl group, cyclopentyl group, vinyl group, allyl group, propenyl group, butenyl group, hexenyl group, cyclohexenyl group and the like can be exemplified. As the substituted alkyl group or alkenyl group, some or all of the hydrogen atoms of these unsubstituted alkyl groups or alkenyl groups are, for example, cyano groups,
The thing substituted by the nitro group, the C1-C5 alkoxy group, etc. can be mentioned. Similarly, examples of the non-aromatic monovalent polycyclic hydrocarbon group having 5 to 12 carbon atoms or the bridged cyclic hydrocarbon group include a cyclopentyl group, a cyclopentenyl group, a cyclohexyl group, a cyclohexenyl group, and a cycloheptyl group. , Cycloheptenyl group, cyclooctyl group, cyclononanyl group, cyclodecanyl group, norbornanyl group, norbornenyl group, isobornanyl group, adamantyl group, adamantylmethylene group, tricyclo [5,2,2]
1,0 ^2,6 ] Decanyl group, tricyclo [5,2,1,0
^2,6 ] decenyl group, tricyclo [5,2,1,0 ^2,6 ] decane methylene group, tetracyclo [4,4,0,1 ^2,5 ,
1 ^7,10 ] dodecanyl group, tetracyclo [4,4,0,1]
^2,5, 1 ^7,10] Dodekeniru group and the like.

In the above equation (1), p1 is a positive number, p2,
p3 and p4 are each 0 or a positive number, and p1 + p2 +
It is a number that satisfies p3 + p4 = 1. That is, p1, p2,
p3 and p4 are repeating units of p1 of the compound of the present invention,
The ratio of the repeating unit of p2, the repeating unit of p3, and the repeating unit of p4 is shown as follows: 0 ≦ p3 / (p1
+ P2 + p3 + p4) ≦ 0.7, preferably 0 ≦ p3 /
(P1 + p2 + p3 + p4) ≦ 0.6, more preferably 0 ≦ p3 / (p1 + p2 + p3 + p4) ≦ 0.5, and if it exceeds 0.7, it becomes insoluble in alkali, and is unsuitable as a base polymer for resist. on the other hand,
If p3 / (p1 + p2 + p3 + p4) is too low, heat resistance may decrease.

Further, 0 <p1 / (p1 + p2 + p3 + p
4) ≦ 0.9, preferably 0.1 ≦ p1 / (p1 + p2
+ P3 + p4) ≦ 0.85, more preferably 0.2 ≦ p
1 / (p1 + p2 + p3 + p4) ≦ 0.8, 0 ≦ p2 /
(P1 + p2 + p3 + p4) ≦ 0.8, preferably 0 ≦
p2 / (p1 + p2 + p3 + p4) ≦ 0.6, more preferably 0 ≦ p2 / (p1 + p2 + p3 + p4) ≦ 0.
5, 0 ≦ p4 / (p1 + p2 + p3 + p4) ≦ 0.9,
Preferably 0 <p4 / (p1 + p2 + p3 + p4) ≦
0.9, more preferably 0.1 ≦ p4 / (p1 + p2 +
p3 + p4) ≦ 0.85, more preferably 0.2 ≦ p4
/(P1+p2+p3+p4)≦0.8. In addition,
When p1 is 0, the contrast of the alkali dissolution rate becomes small and the resolution becomes poor. On the other hand, when it exceeds 0.9, the solubility in alkali is lost, the film thickness is changed during the alkali development, the stress in the film or the generation of bubbles is caused, and the hydrophilic group is decreased, so that the adhesiveness to the substrate is reduced. May be inferior.

The polymeric silicone compound of the present invention is a polymeric silicone compound having a repeating unit represented by the above general formula (1) or a carboxyl group of this polymeric silicone compound or a part of hydrogen atoms of a carboxyl group and a hydroxyl group or Weight average molecular weight of 1,000 which is wholly substituted by one or more kinds of acid labile groups and / or crosslinking groups
.About.50,000. That is, 0 to 100 mol% of the hydrogen atoms of the carboxyl group or the carboxyl group and the hydroxyl group of the polymer silicone compound of the formula (1) is 1 type or 2 types.
It is substituted with one or more acid labile groups.

In this case, various types of acid labile groups are selected, but in particular, a group represented by the following general formula (4), a group represented by the following general formula (5), and a tertiary group having 4 to 20 carbon atoms. An alkyl group, a trialkylsilyl group having 1 to 6 carbon atoms in each alkyl group, and an oxoalkyl group having 4 to 20 carbon atoms are preferably one kind or two or more kinds.

[0064]

[Chemical formula 26]

In the formula, R ⁶ and R ⁷ are a hydrogen atom or a carbon number of 1 to
18, preferably 1 to 6, more preferably 1 to 5, a linear, branched or cyclic alkyl group, and R ⁸ has 1 to 18 carbon atoms, preferably 1 to 10 and more preferably 1 to 8
Represents a monovalent hydrocarbon group which may have a hetero atom such as an oxygen atom, R ⁶ and R ⁷ , R ⁶ and R ⁸ , and R ⁷ and R ⁸ may form a ring, When forming a ring, R ⁶ , R ⁷ , R
⁸ represents a linear or branched alkylene group having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to ⁸ carbon atoms. R ⁹ has 4 to 20 carbon atoms, preferably 4 to 15 carbon atoms,
More preferably, a tertiary alkyl group having 4 to 10 carbon atoms, a trialkylsilyl group in which each alkyl group has 1 to 6 carbon atoms, 4 to 20 carbon atoms, preferably 4 to 15 carbon atoms, and more preferably 4 carbon atoms.
10 represents an oxoalkyl group or a group represented by the above general formula (4). Moreover, a is an integer of 0-6.

R⁶, R⁷C1-C18 straight-chain, branched
Examples of the linear or cyclic alkyl group include R As explained in
Similar groups are mentioned.

R ⁸ is a linear, branched or cyclic alkyl group, phenyl group, p-methylphenyl group, p-
Unsubstituted or substituted aryl groups such as ethyl-phenyl groups and alkoxy-substituted phenyl groups such as p-methoxyphenyl groups, aralkyl groups such as benzyl groups and phenethyl groups, etc., and oxygen atoms in these groups, or bonded to carbon atoms Examples thereof include a group such as an alkyl group represented by the following formula in which a hydrogen atom is substituted with a hydroxyl group or two hydrogen atoms are substituted with oxygen atoms to form a carbonyl group.

[0068]

[Chemical 27]

The tertiary alkyl group having 4 to 20 carbon atoms represented by R ⁹ is tert-butyl group, 1-methylcyclohexyl group, 2- (2-methyl) adamantyl group, te
An rt-amyl group etc. can be mentioned.

Examples of the trialkylsilyl group having 1 to 6 carbon atoms in each alkyl group include a trimethylsilyl group, a triethylsilyl group and a dimethyl-tert-butyl group, and examples of the oxoalkyl group having 4 to 20 carbon atoms include , 3-
Examples thereof include an oxocyclohexyl group and a group represented by the following formula.

[0071]

[Chemical 28]

Specific examples of the acid labile group represented by the above formula (4) include 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-
Amyloxyethyl group, 1-ethoxy-n-propyl group,
1-cyclohexyloxyethyl group, methoxypropyl group, ethoxypropyl group, 1-methoxy-1-methyl-
Ethyl group, linear or branched acetal group such as 1-ethoxy-1-methyl-ethyl group, tetrahydrofuranyl group, cyclic acetal group such as tetrahydropyranyl group, and the like, preferably ethoxyethyl group, butoxyethyl group Group, an ethoxypropyl group. On the other hand, as the acid labile group of the above formula (5), for example, tert-butoxycarbonyl group, tert-butoxycarbonylmethyl group, tert-amyloxycarbonyl group, tert-amyloxycarbonylmethyl group, 1-ethoxyethoxycarbonylmethyl group. , 2-tetrahydropyranyloxycarbonylmethyl group, 2-tetrahydrofuranyloxycarbonylmethyl group and the like.

The rate of introduction of the acid labile group is determined by the above formula (1).
When the high molecular silicone compound of 1 is used as a base resin of a positive resist material, the amount is more than 0 mol% and not more than 100 mol%, more preferably 20 to 98 mol%, further preferably 30 to 95% of the total hydrogen atoms of the carboxyl group. Mol%
And the total number of hydrogen atoms in the hydroxyl group is 0 to 1
The amount is preferably 00 mol%, more preferably 0 to 80 mol%, still more preferably 0 to 60 mol%. If the hydrogen atom of the carboxyl group is not replaced with the acid labile group (the introduction rate of the acid labile group to the hydrogen atom of the carboxyl group is 0 mol%), the contrast of the alkali dissolution rate becomes small and the resolution becomes poor.

On the other hand, when the polymeric silicone compound of the above formula (1) is used as a base resin for a negative resist material, the introduction rate of the acid labile group is 0 to 90 mol% of the total hydrogen atoms of the carboxyl group. It is preferably 0 to 80 mol%, more preferably 0 to 70 mol%.
It is also preferable that the total amount of hydrogen atoms in the hydroxyl group is 0 to 70 mol%, more preferably 0 to 60 mol%, and further preferably 0 to 50 mol%.

Further, in the polymer silicone compound of the present invention, a part or all of hydrogen atoms of a carboxyl group or a carboxyl group and a hydroxyl group are contained in an amount of 0 mol% to 100 mol% due to one or more kinds of acid labile groups. The remaining hydrogen atoms of the carboxyl group and / or the hydroxyl group of the polymer silicone compound represented by the general formula (1) substituted by the ratio are more than 0 mol% and not more than 50 mol% of the total hydrogen atoms of the carboxyl group and the hydroxyl group. , More preferably 0.2 to 40 mol%, and even more preferably 0.25 to 30 mol% with a group having a C—O—C group represented by the following general formula (3a) or (3b). It may be crosslinked intramolecularly and / or intermolecularly.

[0076]

[Chemical 29] (In the formula, R ³ and R ⁴ represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms. Alternatively, R ³ and R ⁴ may form a ring, When forming a ring, R ³ and R ^{4 each} represent a linear or branched alkylene group having 1 to 8 carbon atoms, and R ⁵ represents a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms. Group, 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, The group of may have a heteroatom interposed,
Further, a part of hydrogen atoms bonded to the carbon atom is a hydroxyl group,
It may be substituted with a carboxyl group, an acyl group or a fluorine atom. B is -CO-O-, -NHCO-O
-Or-NHCONH- is shown. c is 2-8, c'is 1
Is an integer of ~ 7. )

Here, as the linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, the same ones as described above can be exemplified. Examples of the linear, branched or cyclic alkylene group having 1 to 10 carbon atoms of R ⁵ include methylene group, ethylene group, propylene group, isopropylene group, n
-Butylene group, isobutylene group, cyclohexylene group,
A cyclopentylene group etc. can be illustrated. In addition,
A specific example of A will be described later. The crosslinkable groups (3a) and (3b)
Is derived from an alkenyl ether compound and a halogenated alkyl ether compound described later.

The bridging group is not limited to divalent, as is clear from the value of c'in the above formulas (3a) and (3b), but is not limited to trivalent.
It may be an octavalent group. For example, as the divalent bridging group, the following formulas (3a ′) and (3b ′) can be given as the trivalent bridging group.
Examples include those represented by the following formulas (3a ″) and (3b ″).

[0079]

[Chemical 30] The preferred cross-linking group is represented by the following general formula (3a ′ ″) or (3b ′ ″).

[0080]

[Chemical 31] (In the formula, R ³ and R ⁴ represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms. Alternatively, R ³ and R ⁴ may form a ring, When forming a ring, R ³ and R ^{4 each} represent a linear or branched alkylene group having 1 to 8 carbon atoms, and R ⁵ represents a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms. Group, 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. Alternatively, it represents an arylene group having 6 to 30 carbon atoms, and these groups may have a heteroatom interposed therebetween,
Further, a part of hydrogen atoms bonded to the carbon atom is a hydroxyl group,
It may be substituted with a carboxyl group, an acyl group or a fluorine atom. B is -CO-O-, -NHCO-O
-Or-NHCONH- is shown. c '' is 2-4,
c ″ ′ is an integer of 1 to 3. )

As the polymeric silicone compound of the present invention, those having a repeating unit represented by the following general formula (1a) are preferable.

[0082]

[Chemical 32]

In the formula, R ⁰ represents the above-mentioned acid labile group.
p11 + p12 = p1, p11 ≧ 0, p12> 0, preferably 0 <p12 / p1 ≦ 1, more preferably 0.2 ≦ p12 / p1 ≦ 0.98, and even more preferably 0.
3 ≦ p12 / p1 ≦ 0.95. Also, p41 + p
42 = p4, p41> 0 and p42 ≧ 0. In this case, it is preferable that 0 <(p12 + p42) / (p1 + p4) ≦ 1, more preferably 0.05 ≦ (p12
+ P42) / (p1 + p4) ≦ 0.9, more preferably 0.1 ≦ (p12 + p42) / (p1 + p4) ≦ 0.8
Is. In addition, Z, Z ', x, y, z, R ¹ , R ² , p
1, p2, p3 and p4 are as described above.

Further, examples of the polymeric silicone compound having a C—O—C group-containing crosslinking group of the present invention include those represented by the following formulas (1b) to (1e). The following examples are examples in which x, y, and z are each 1. The compounds of formulas (1b) and (1d) are intermolecular bonds, and the formulas (1c) and (1e) are intramolecular bonds. However, the present invention is not limited to the following examples.

[0085]

[Chemical 33]

[0086]

[Chemical 34]

[0087]

[Chemical 35]

[0088]

[Chemical 36]

In the above formula, Q is a bridging group having a C—O—C group, typically a bridging group represented by the above formula (3a) or (3b), particularly formulas (3a ′) and (3b ′). And (3
a ″), (3b ″), preferably (3a ′ ″),
It is a crosslinking group represented by (3b ′ ″). In this case, when the bridging group is trivalent or higher, Q is bonded to 3 or more of the following units in the above formula.

[0090]

[Chemical 37]

Further, in the above formulas (1b) to (1e), p111 + p112 = p11, p411 + p412
= P41, 0 ≦ p112 / p1 ≦ 0.5, 0 ≦ p
412 / p4 ≦ 0.5, 0 ≦ (p112 + p412) /
It is preferable that (p1 + p4) ≦ 0.5, and more preferably 0.002 ≦ p112 / p1 ≦ 0.5, 0 ≦ p.
412 / p4 ≦ 0.4, 0.001 ≦ (p112 + p4
12) / (p1 + p4) ≦ 0.45, more preferably 0.0025 ≦ p112 / p1 ≦ 0.4, 0 ≦ p4
12 / p4 ≦ 0.3, 0.001 ≦ (p112 + p41
2) / (p1 + p4) ≦ 0.4. In addition, (p12
+ P112 + p42 + p412) / (p1 + p4) is 0
Is more than 1 and is 1 or less, more preferably 0.05 to 0.9, and further preferably 0.1 to 0.8.

When the proportion of the cross-linking group having a C—O—C group is 0 mol%, the contrast of the alkali dissolution rate becomes small, the advantages of the cross-linking group cannot be brought out, and the resolution may deteriorate. Yes, on the other hand, if too much is cross-linked and gels, loses solubility in alkali, causes film thickness change or film stress or bubble generation during alkali development, and reduces hydrophilic groups. In some cases, the adhesion to the substrate is poor.

When the ratio of the acid labile group is 0 mol%, the contrast of the alkali dissolution rate becomes small and the resolution becomes poor. On the other hand, if the amount is too large, the solubility in alkali may be lost, or the affinity with the developing solution may decrease during alkali development, resulting in poor resolution.

In this case, the dimension of the pattern and the shape of the pattern can be arbitrarily controlled by appropriately selecting the values of the crosslinkable group having a C—O—C group and the acid labile group within the above range. . In the polymeric silicone compound of the present invention, the content of the cross-linking group having a C—O—C group and the acid labile group affects the contrast of the dissolution rate of the resist film, and the resist material such as pattern size control and pattern shape Related to the characteristics of.

Here, the above-mentioned polymer silicone compound may have two or more kinds of acid labile groups in the molecule, or may blend two or more kinds of polymers having different acid labile groups.

In this case, the above equations (1a) to (1e)
In the unit (u-1) having the following acid labile group,
As (u-2), the following groups (u-1 ′) and (u
-2 ') is preferable.

[0097]

[Chemical 38]

In the above formula, p121 + p122 = p12, and p121 / p12 is 0 to 1, more preferably 0.05 to 1, and still more preferably 0.1 to 1. Also, p421 + p422 = p42, and p421 / p
42 is 0 to 1, more preferably 0.05 to 1, and still more preferably 0.1 to 1, but (p121 + p42
1) / (p12 + p42) is 0 to 1, more preferably 0.05 to 1, and further preferably 0.1 to 1.

The polymer silicone compound of the present invention has a weight average molecular weight of 1,000 to 50,000, preferably 1,500 to 30,000. If the weight average molecular weight is less than 1,000, the resist material is inferior in heat resistance, and if it exceeds 50,000, the resist material cannot be applied uniformly during spin coating.

Next, the method for producing the polymeric silicone compound of the present invention will be described. This polymeric silicone compound has a divalent to dicarboxylic acid alkyl ester group-bonded group.
Hexavalent C5-C12 Non-Aromatic Monocyclic or Polycyclic Hydrocarbon Group or Bridged Cyclic Hydrocarbon Group-Containing Trichlorosilane Compound and Alkylcarbonyloxy Group-Bivalent to Hexavalent Having a linear or branched hydrocarbon group having 1 to 20 carbon atoms, or a non-aromatic monocyclic or polycyclic hydrocarbon group having 3 to 20 carbon atoms or a bridged cyclic hydrocarbon group Trichlorosilane compound, further hydrolyzing a trichlorosilane compound having a linear, branched or cyclic alkyl group as necessary, after further thermally condensing the hydrolysis condensate, the alkyl ester group and alkylcarbonyloxy group Hydrolysis (KOH,
NaOH or the like) to obtain a polymer silicone compound represented by the following formula (1 ′). In consideration of storage stability, trimethylsilylation is preferable in order to protect the silanol group at the end of the main chain. By introducing an acid labile group into the carboxyl group of the obtained polymer silicone compound, the intended polymer silicone compound can be obtained. Alternatively, the desired polymer silicone compound can be obtained by introducing an acid labile group of R ^0, a group of R ¹ or a cross-linking group into the carboxyl group and the hydroxyl group. The introduction of the R ¹ group can be carried out by a conventional method. For example, when R ¹ has an ester structure represented by the general formula (2a), a synthetic method by dehydration reaction using an acid catalyst,
Examples include a method via an active ester such as trifluoroacetic anhydride or dicyclohexylcarbodiimide, a method of activating an alcohol such as diethyl azodicarboxylate, and a method using an O-alkylating agent such as diazoalkane. .

On the other hand, when R ¹ has an amide structure represented by the general formula (2b), a method or activity using a condensing agent such as dicyclohexylcarbodiimide or N-ethyl-N′-3-dimethylaminopropylcarbodiimide is used. Examples thereof include a method via an ester p-nitrophenyl ester and an azide method via a peptide hydrazide.

[0102]

[Chemical Formula 39] (In the formula, Z, Z ′, R ² , p1, p2, p3, p4,
x and z have the same meanings as above. )

The acid labile group can be introduced by a known method. Moreover, as a method of crosslinking with a crosslinking group having a C—O—C group, a method using an alkenyl ether compound or a halogenated alkyl ether compound can be mentioned.

That is, as a method for producing the polymeric silicone compound of the present invention having a cross-linking group having a C--O--C group, the carboxyl group of the polymeric silicone compound (1 ') obtained by the above polymerization method is used. Alternatively, by introducing an acid labile group represented by the general formula (4) into the carboxyl group and the hydroxyl group,
After isolation, a method of crosslinking with an intramolecular and / or intermolecular crosslinking group having a C—O—C group by reaction with an alkenyl ether compound or a halogenated alkyl ether compound, or an alkenyl ether compound or a halogenated alkyl ether compound A method of cross-linking intramolecularly and / or intermolecularly with a group represented by C—O—C by reaction with and then introducing an acid labile group represented by the general formula (4), or an alkenyl ether compound Alternatively, there may be mentioned a method in which the reaction with a halogenated alkyl ether compound and the introduction of the acid labile group represented by the general formula (4) are carried out at once, and the reaction with an alkenyl ether compound or a halogenated alkyl ether compound and the general formula ( 4)
The method of collectively introducing the acid labile group represented by is preferable. Further, if necessary, an acid labile group represented by the general formula (5), a tertiary alkyl group, a trialkylsilyl group, an oxoalkyl group, or the like may be introduced into the polymer silicone compound thus obtained. It is possible.

Specifically, as a first method, a polymer silicone compound having a repeating unit represented by the above formula (1 ′) and an alkenyl ether compound represented by the following general formula (I) or (II), As a method using a compound represented by the following general formula (4a) and a second method, a polymer silicone compound having a repeating unit represented by the above formula (1 ′) and the following general formula (VII) or (VIII)
Examples of the method include using a halogenated alkyl ether compound represented by and a compound represented by the following general formula (4b).

[0106]

[Chemical 40]

Here, Z, Z ', R ² , p1, p2, p
3, p4, x, z and ^{R 4, R 5, R 7} , R 8 represents the same meaning as above and, R ^3a, R ^6a is a hydrogen atom or a number 1-7 linear, branched Represents a linear or cyclic alkyl group.

Further, in the vinyl ether compound represented by the formula (I) or (II), A is an aliphatic or alicyclic saturated hydrocarbon group having a c value (c is 2 to 8) and having 1 to 50 carbon atoms. , An aromatic hydrocarbon group or a heterocyclic group, B
Is -CO-O-, -NHCOO- or -NHCONH-
R ⁵ 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 or aromatic hydrocarbon group of A is preferably O, NH, N having 1 to 50 carbon atoms, particularly 1 to 40 carbon atoms.
(CH ₃ ), S, SO _2, etc., which may have an intervening heteroatom, such as an unsubstituted or hydroxyl group, a carboxyl group, an acyl group or a fluorine atom-substituted alkylene group, preferably having 6 to 5 carbon atoms.
0, especially 6 to 40 arylene groups, groups in which these alkylene groups and arylene groups are bonded, and c '' valence (c) is 3 to 8 in which a hydrogen atom bonded to a carbon atom of each of the above groups is eliminated.
An integer) and a c-valent heterocyclic group, a group in which this heterocyclic group is bonded to the above hydrocarbon group, and the like.

Illustrative examples of A include the following.

[0111]

[Chemical 41]

[0112]

[Chemical 42]

[0113]

[Chemical 43]

[0114]

[Chemical 44]

The compound represented by the general formula (I) can be obtained by, for example, Stephen. C. Lapin, Polymer
s Paint Color Journal. 17
9 (4237), 321 (1988), that is, synthesis by reaction of polyhydric alcohol or polyhydric phenol with acetylene, or reaction of polyhydric alcohol or polyhydric phenol with halogenated alkyl vinyl ether. You can

Specific examples of the compound of 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) Examples of the compound include, but are not limited to.

[0117]

[Chemical formula 45]

[0118]

[Chemical formula 46]

[0119]

[Chemical 47]

[0120]

[Chemical 48]

[0121]

[Chemical 49]

On the other hand, the compound represented by the above general formula (II) when B is —CO—O— 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 terephthalic acid diethylene vinyl ether, phthalic acid diethylene vinyl ether, isophthalic acid diethylene vinyl ether, phthalic acid dipropylene vinyl ether, and terephthalic acid dipropylene vinyl ether. Examples thereof include, but are not limited to, isophthalic acid dipropylene vinyl ether, maleic acid diethylene vinyl ether, fumaric acid diethylene vinyl ether, and itaconic acid diethylene vinyl ether.

Further, as the alkenyl ether group-containing compound preferably used in the present invention, an alkenyl ether compound having an active hydrogen represented by the following general formula (III), (IV) or (V) and an isocyanate group can be used. Examples thereof include an alkenyl ether group-containing compound synthesized by reaction with a compound having the same.

[0124]

[Chemical 50] (R ^3a , R ⁴ and R ⁵ have the same meanings as above.)

B is --NHCOO-- or --NHCONH--
In this case, as the compound having an isocyanate group represented by the general formula (II), for example, the compounds described in Crosslinking Agent Handbook (Taiseisha, 1981) can be used. Specifically, triphenylmethane triisocyanate, diphenylmethane diisocyanate, tolylene diisocyanate, dimer of 2,4-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-tolylene diisocyanate. Nato, polymethylene polyphenyl isocyanate, polyisocyanate type such as hexamethylene diisocyanate, adduct of tolylene diisocyanate and trimethylolpropane, adduct of hexamethylene diisocyanate and water, xylene diisocyanate Examples thereof include polyisocyanate adduct types such as adducts with trimethylolpropane. By reacting the above-mentioned isocyanate group-containing compound with the active hydrogen-containing alkenyl ether compound, various compounds having an alkenyl ether group at the terminal can be prepared. As such compounds, the following formulas (II-1) to (II-1
Examples thereof include, but are not limited to, those shown in 1).

[0126]

[Chemical 51]

[0127]

[Chemical 52]

In the first method, when a polymer silicone compound cross-linked with a cross-linking group having a C—O—C group is obtained, the weight average molecular weight is 1,000 to 50,000, preferably the general formula 1 of the carboxyl group or the carboxyl group and the hydroxyl group of the polymer compound represented by (1 ′)
P112 + p412 mol of the general formula (I), based on mol;
Alkenyl ether compound represented by (II) and p1
By reacting 2 + p42 mol of the compound represented by the general formula (4a), for example, the following general formulas (3a′-1) and (3a ′)
A polymer compound represented by -2) can be obtained.

[0129]

[Chemical 53]

[0130]

[Chemical 54]

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

The catalyst acid is preferably hydrochloric acid, sulfuric acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, p-toluenesulfonic acid pyridinium salt, etc. It is preferably 0.1 to 10 mol% with respect to 1 mol of the carboxyl 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
It is 00 hours, preferably 0.5 to 20 hours.

When the above reactions are carried out collectively without isolation,
The order of adding the alkenyl ether compound represented by the general formula (I) or (II) and the compound represented by the general formula (4a) is not particularly limited, but the compound represented by the general formula (4a) is first added, It is preferable to add the alkenyl ether compound represented by the general formula (I) or (II) after the reaction has sufficiently proceeded. For example, the alkenyl ether compound represented by the general formula (I) or (II) and the compound represented by the general formula (4a) are simultaneously added, or the alkenyl ether compound represented by the general formula (I) or (II) is added first. When added, the general formula (I) or (II)
In some cases, some of the reaction points of the alkenyl ether compound represented by are hydrolyzed by water in the reaction system, the structure of the produced polymer compound becomes complicated, and it becomes difficult to control the physical properties.

[0135]

[Chemical 55] (In the formula, Z, Z ′, R ² , p1, p2, p3, p4,
x, z and R ⁵ , R ^6a , R ⁷ , R ⁸ , c and d have the same meanings as described above, and D is a halogen atom (Cl, Br).
Or I). )

The compounds of the formulas (VI) and (VII) and the compound of the formula (4b) are obtained by adding hydrogen chloride and hydrogen bromide to the compounds of the formulas (I) and (II) and the formula (4a). Alternatively, it can be obtained by reacting hydrogen iodide.

In the second method, when a crosslinked polymer silicone compound is obtained, the weight average molecular weight is 1,000 to 50.
P112 + p412 with respect to 1 mol of the carboxyl group or the carboxyl group and the hydroxyl group of the polymer compound having the repeating unit represented by the above general formula (1 ′).
For example, the halogenated alkyl ether compound represented by the general formula (VI) or (VII) and p12 + p42 mol of the compound represented by the general formula (4b) are reacted with each other to give, for example, the above formula (3a′-1) or (3a ′). A polymer compound represented by -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, and they are 2
You may mix and use 1 or more types.

As the base, triethylamine, pyridine, diisopropylamine, potassium carbonate and the like are preferable, and the amount used is 1 mole times the mole of the carboxyl group of the polymer compound represented by the general formula (1 ′) to react. As described above, the molar ratio is preferably 5 times or more.

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

As described above, the polymer compound having the repeating unit represented by the formula (1 ′) or the polymer compound in which a part of the carboxyl group thereof is replaced by the COR ¹ group is added to the formula (4a) or (4b). A compound having an acid labile group, for example, a compound represented by the following formula (1 ″)
After the compound represented by the formula (1) is obtained, it may be isolated, and then the compound represented by the formula (I), (II) or (VI), (VII) may be used for crosslinking.

[0142]

[Chemical 56]

If necessary, the polymer compound obtained by the first or second method, for example, the compound represented by the formula (3a′-1) or (3a′-2) may be added to the original general formula (1 ′). ) Introduce the acid labile group represented by the general formula (5) by reacting p122 + p422 mol of dialkyl dicarbonate compound, alkoxycarbonylalkyl halide, etc. with 1 mol of the carboxyl group of the polymer compound represented by By reacting a tertiary alkyl halide, a trialkylsilyl halide, an oxoalkyl compound, etc., for example, the compound of the general formula (3b ′
It is possible to obtain the polymer compounds represented by -1) and (3b'-2).

[0144]

[Chemical 57]

[0145]

[Chemical 58]

The method of introducing the acid labile group of the above formula (5) is as follows:
It is preferably carried out in the presence of a base in a solvent.

As the reaction solvent, acetonitrile, acetone, dimethylformamide, dimethylacetamide,
An aprotic polar solvent such as tetrahydrofuran or dimethylsulfoxide is preferable, and they may be used alone or in combination of two or more.

As the base, triethylamine, pyridine, imidazole, diisopropylamine, potassium carbonate and the like are preferable, and the amount of the base used is 1 mol with respect to 1 mol of the carboxyl group of the polymer represented by the general formula (1 ′). It is preferably a molar ratio or more, and particularly preferably a molar ratio of 5 or more.

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

Examples of the dialkyl dicarbonate compound include di-tert-butyl dicarbonate and di-tert-amyl dicarbonate, and examples of the alkoxycarbonylalkyl halide include tert-butoxycarbonylmethyl chloride.
tert-amyloxycarbonylmethyl chloride, t
ert-butoxycarbonylmethyl bromide, ter
Examples thereof include t-butoxycarbonylethyl chloride, and examples of the trialkylsilyl halide include trimethylsilyl chloride, triethylsilyl chloride, dimethyl-tert-butylsilyl chloride and the like.

The polymer compounds represented by the general formulas (3a'-1) and (3a'-2) obtained by the first or second method may be added to the original general formula (1) if necessary. It is possible to carry out tertiary alkylation or oxoalkylation by reacting p12 + p42 mols of a tertiary alkylating agent or an oxoalkyl compound with 1 mol of the carboxyl group of the polymer compound represented by ').

The above method is preferably carried out in the presence of an acid in a solvent. The reaction solvent is preferably an aprotic polar solvent such as dimethylformamide, dimethylacetamide, tetrahydrofuran, ethyl acetate,
You may use it individually or in mixture of 2 or more types.

The catalyst acid is preferably hydrochloric acid, sulfuric acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, p-toluenesulfonic acid pyridinium salt, etc. ) With respect to 1 mol of the carboxyl group of the polymer compound represented by
It is preferably 1 to 10 mol%.

The reaction temperature is −20 to 100 ° C., preferably 0 to 60 ° C., and the reaction time is 0.2 to 1
It is 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 can be mentioned, and as the oxoalkyl compound, α-angelicalactone, 2-cyclohexen-1-one, 5,6-
Dihydro-2H-pyran-2-one and the like can be mentioned.

The general formulas (3a'-1) and (3a'-
The polymer compound having the repeating unit represented by the following general formula (3c′-1) or (3c′-2) is directly added to the acid compound represented by the general formula (5) without passing through the polymer compound represented by 2). Unstable group, tertiary alkyl group, trialkylsilyl group,
After introducing the oxoalkyl group and the like, the acid labile group represented by the general formula (4) can be introduced, if necessary.

[0157]

[Chemical 59]

[0158]

[Chemical 60]

In the polymer compound of the present invention, the acid labile group for R ² is not limited to one type, and two or more types can be introduced. In this case, p41 mol of the acid labile group is introduced into 1 mol of all the hydroxyl groups of the polymer compound of the formula (1 ′) as described above, and then an acid labile group different from this is introduced in the same manner as above. Introducing p42 mol of the above compound makes it possible to obtain a polymer compound in which two or more kinds of such acid labile groups are introduced or by repeating such an operation as appropriate.

The polymeric silicone compound of the present invention is effective as a base polymer of a resist material, and the resist material of the present invention contains this polymeric silicone compound as a base polymer. In this case, the resist material may be a positive type or a negative type, but is preferably a chemically amplified type. Examples of such a resist material include (A) an organic solvent, (B) a base resin as the above-mentioned polymer silicone compound, (C) an acid generator, and, if necessary, (D) a dissolution controller, (E) a basic compound. , (F) a compound having a group represented by ≡C-COOH in the molecule, (G) a chemically amplified positive resist material containing an acetylene alcohol derivative, (A) an organic solvent, and (B) a base resin having the above-mentioned properties. Examples thereof include a chemically amplified negative resist material containing a molecular silicone compound, a (C) acid generator, and a compound that is crosslinked by the action of (H) acid.

Here, the organic solvent of the component (A) used in the present invention may be any organic solvent in which the acid generator, the base resin, the dissolution control agent and the like can be dissolved. Examples of such an organic solvent include ketones such as cyclohexanone and methyl-2-n-amyl ketone, 3-methoxybutanol, 3-methyl-3-methoxybutanol,
1-methoxy-2-propanol, 1-ethoxy-2-
Alcohols such as propanol, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether and other ethers, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether Acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate,
Esters such as ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, and propylene glycol-mono-tert-butyl ether acetate may be mentioned, and one of these may be used alone or two or more thereof may be mixed. It can be used, but is not limited to these. In the present invention, among these organic solvents, in addition to diethylene glycol dimethyl ether and 1-ethoxy-2-propanol, which have the best solubility of the acid generator in the resist component, propylene glycol monomethyl ether acetate which is a safe solvent and a mixture thereof. Solvents are preferably used.

The amount of the organic solvent used is 200 to 100 parts by weight of the base resin of the component (B) (parts by weight; the same applies hereinafter).
1,000 parts, especially 400 to 800 parts are preferred.
Examples of the acid generator as the component (C) include the following general formulas (6a-1), (6a-2) or (6b).
Onium salt, a diazomethane derivative of the following general formula (7), a glyoxime derivative of the following general formula (8), a bissulfone derivative of the following general formula (9), and a sulfonic acid ester of an N-hydroxyimide compound of the following general formula (10). , Β-ketosulfonic acid derivatives, disulfone derivatives, nitrobenzyl sulfonate derivatives, sulfonic acid ester derivatives and the like.

[0163]

[Chemical formula 61] (In the formula, R ^30a , R ^30b , and R ^30c each have 1 to 1 carbon atoms.
2 represents a linear, branched or cyclic alkyl group, alkenyl group, oxoalkyl group or oxoalkenyl group, aryl group having 6 to 20 carbon atoms or aralkyl group or aryloxoalkyl group having 7 to 12 carbon atoms, Some or all of the hydrogen atoms of these groups may be substituted with an alkoxy group or the like. R ^30b and R ^30c may form a ring, and in the case of forming a ring, R ^30b and R ^30c each represent an alkylene group having 1 to 6 carbon atoms, and K ⁻ is a non-nucleophilic group. Represents a counter ion. )

The above R ^30a , R ^30b and R ^30c may be the same or different from each other. Specifically, as the alkyl group, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclopropylmethyl group, 4-methylcyclohexyl group, cyclohexylmethyl group, norbornyl group,
Examples thereof include an adamantyl group. As the alkenyl group, a vinyl group, an allyl group, a propenyl group, a butenyl group,
Examples thereof include a hexenyl group and a cyclohexenyl group. Examples of the oxoalkyl group and the oxoalkenyl group include a 2-oxocyclopentyl group and a 2-oxocycloheptyl group, and a 2-oxopropyl group, a 2-cyclopentyl-2-oxoethyl group, a 2-cyclohexyl-2 group.
-Oxoethyl group, 2- (4-methylcyclohexyl)
A 2-alkyl-2-oxoethyl group such as a 2-oxoethyl group can be mentioned. Examples of the aryl group include phenyl group, naphthyl group, p-methoxyphenyl group,
Alkoxyphenyl groups such as m-methoxyphenyl group, o-methoxyphenyl group, ethoxyphenyl group, p-tert-butoxyphenyl group, m-tert-butoxyphenyl group, 2-methylphenyl group, 3-methylphenyl group, 4 -Methylphenyl group, ethylphenyl group, 4-
tert-butylphenyl group, 4-butylphenyl group,
Alkylphenyl groups such as dimethylphenyl group, alkylnaphthyl groups such as methylnaphthyl group and ethylnaphthyl group,
Methoxynaphthyl group, alkoxynaphthyl group such as ethoxynaphthyl group, dialkylnaphthyl group such as dimethylnaphthyl group, diethylnaphthyl group, dimethoxynaphthyl group,
Examples thereof include dialkoxynaphthyl groups such as diethoxynaphthyl group. Examples of the aralkyl group include a benzyl group, a phenylethyl group and a phenethyl group. Examples of the aryloxoalkyl group include 2- (phenyl) -2-oxoethyl group, 2- (1-naphthyl) -2-oxoethyl group, 2- (2-naphthyl) -2-oxoethyl group and the like.
-Aryl-2-oxoethyl group and the like. K ^-
Examples of the non-nucleophilic counter ion include chloride ion, halide ion such as bromide ion, triflate, perfluorooctyl sulfonate, 1,1,1-trifluoroethane sulfonate, fluoroalkyl sulfonate such as nonafluorobutane sulfonate, and tosylate. , Benzene sulfonate, 4-fluorobenzene sulfonate, 4
-Trifluoromethylbenzenesulfonate, 1,2,
Examples thereof include aryl sulfonates such as 3,4,5-pentafluorobenzene sulfonate, and alkyl sulfonates such as mesylate and butane sulfonate.

[0165]

[Chemical formula 62] (In the formula, R ^31a and R ^31b are each a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, and R ³² is 1 to 1 carbon atoms.
A linear, branched or cyclic alkylene group of 0, R ^33a ,
R ^33b each represents a 2-oxoalkyl group having 3 to 7 carbon atoms, and K ⁻ represents a non-nucleophilic counter ion. )

Specific examples of R ^31a and R ^31b include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group and heptyl group. , Octyl group, cyclopentyl group, cyclohexyl group, cyclopropylmethyl group, 4-methylcyclohexyl group, cyclohexylmethyl group and the like. R ³² is a methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, 1,4-cyclohexylene group, 1,2-cyclohexylene. Group, 1,3-cyclopentylene group, 1,4-cyclooctylene group, 1,4-cyclohexanedimethylene group and the like. ^{Examples of} R ^33a and R ^33b include a 2-oxopropyl group, a 2-oxocyclopentyl group, a 2-oxocyclohexyl group, and a 2-oxocycloheptyl group. Examples of K ⁻ include the same as in formula (6a).

[0167]

[Chemical formula 63] (In the formula, R ³⁴ and R ³⁵ are a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms or a halogenated alkyl group, an aryl group having 6 to 20 carbon atoms, a halogenated aryl group or a carbon number 7 ~ Represents an aralkyl group of 12.)

The alkyl groups of R ³⁴ and R ³⁵ include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group and octyl group. Group, amyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, norbornyl group, adamantyl group and the like. As the halogenated alkyl group, trifluoromethyl group, 1,1,1-trifluoroethyl group, 1,1,1-
Examples thereof include trichloroethyl group and nonafluorobutyl group. As the aryl group, a phenyl group, a p-methoxyphenyl group, an m-methoxyphenyl group, an o-methoxyphenyl group, an ethoxyphenyl group, an alkoxyphenyl group such as a p-tert-butoxyphenyl group and an m-tert-butoxyphenyl group, Examples thereof include alkylphenyl groups such as 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, ethylphenyl group, 4-tert-butylphenyl group, 4-butylphenyl group and dimethylphenyl group. Examples of the halogenated aryl group include a fluorobenzene group, a chlorobenzene group and a 1,2,3,4,5-pentafluorobenzene group. Examples of the aralkyl group include a benzyl group and a phenethyl group.

[0169]

[Chemical 64] (In the formula, R ³⁶ , R ³⁷ , and R ³⁸ are linear groups having 1 to 12 carbon atoms,
It represents a branched or cyclic alkyl group or halogenated alkyl group, an aryl group having 6 to 20 carbon atoms, a halogenated aryl group or an aralkyl group having 7 to 12 carbon atoms. Also,
R ³⁷ and R ³⁸ may combine with each other to form a cyclic structure, and when forming a cyclic structure, R ³⁷ and R ³⁸ each represent a linear or branched alkylene group having 1 to 6 carbon atoms. . )

Examples of the alkyl group, halogenated alkyl group, aryl group, halogenated aryl group and aralkyl group for R ³⁶ , R ³⁷ and R ³⁸ include the same groups as those described for R ³⁴ and R ³⁵ . ^Examples of the alkylene group for R ³⁷ and R ³⁸ include a methylene group, an ethylene group, a propylene group, a butylene group and a hexylene group.

[0171]

[Chemical 65] (In the formula, R ^30a and R ^30b are the same as above.)

[0172]

[Chemical formula 66] (In the formula, R ³⁹ represents an arylene group having 6 to 10 carbon atoms, an alkylene group having 1 to 6 carbon atoms, or an alkenylene group having 2 to 6 carbon atoms, and some or all of hydrogen atoms of these groups are further carbon atoms. It may be substituted with a linear or branched alkyl group or alkoxy group having a number of 1 to 4, a nitro group, an acetyl group, or a phenyl group, and R ⁴⁰ is a linear or branched group having a carbon number of 1 to 8. Or a substituted alkyl group, an alkenyl group, an alkoxyalkyl group, a phenyl group, or a naphthyl group, and some or all of the hydrogen atoms of these groups further have 1 to 4 carbon atoms.
Alkyl group or alkoxy group; a phenyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms, an alkoxy group, a nitro group or an acetyl group; a heteroaromatic group having 3 to 5 carbon atoms; or a fluorine atom, chlorine It may be substituted with an atom. )

Here, the arylene group for R ³⁹ is
1,2-phenylene group, 1,8-naphthylene group and the like, and as the alkylene group, methylene group, 1,2-ethylene group, 1,3-propylene group, 1,4-butylene group, 1-
Phenyl-1,2-ethylene group, norbornane-2,3
Examples of the alkenylene group such as -diyl group include 1,2-vinylene group, 1-phenyl-1,2-vinylene group, and 5-norbornene-2,3-diyl group. Examples of the alkyl group of R ⁴⁰ are the same as those of R ^{30a to} R ^30c, and examples of the alkenyl group are vinyl group, 1-propenyl group, allyl group, 1-butenyl group, 3-butenyl group, isoprenyl group, 1- Pentenyl group, 3-pentenyl group, 4-pentenyl group, dimethylallyl group, 1-hexenyl group, 3-
Hexenyl group, 5-hexenyl group, 1-heptenyl group,
A 3-heptenyl group, a 6-heptenyl group, a 7-octenyl group and the like are alkoxyalkyl groups such as a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a butoxymethyl group, a pentoxymethyl group, a hexyloxymethyl group and a hexyloxymethyl group. Propyloxymethyl group, methoxyethyl group, ethoxyethyl group, propoxyethyl group, butoxyethyl group,
Pentoxyethyl group, hexyloxyethyl group, methoxypropyl group, ethoxypropyl group, propoxypropyl group, butoxypropyl group, methoxybutyl group, ethoxybutyl group, propoxybutyl group, methoxypentyl group,
Examples thereof include an ethoxypentyl group, a methoxyhexyl group and a methoxyheptyl group.

The number of carbon atoms which may be further substituted is 1
Examples of the linear or branched alkyl group of 4 to 4 include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a tert-butyl group, and an alkoxy group includes a methoxy group. An ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a tert-butoxy group, etc., which may be substituted with an alkyl group having 1 to 4 carbon atoms, an alkoxy group, a nitro group or an acetyl group. Examples of the group include a phenyl group, tolyl group, p-tert-butoxyphenyl group, p-acetylphenyl group, p-nitrophenyl group and the like, and examples of the aromatic group include a pyridyl group and a furyl group.

Specifically, for example, diphenyliodonium trifluoromethanesulfonate, (p-tert-butoxyphenyl) phenyliodonium trifluoromethanesulfonate, diphenyliodonium p-toluenesulfonate and p-toluenesulfonic acid (p-tert-butanoic acid).
Butoxyphenyl) phenyliodonium, triphenylsulfonium trifluoromethanesulfonate, trifluoromethanesulfonate (p-tert-butoxyphenyl) diphenylsulfonium, bis (p-tert-butoxyphenyl) phenylsulfonium trifluoromethanesulfonate, trifluoromethanesulfonate tris (P-tert-butoxyphenyl) sulfonium,
Triphenylsulfonium p-toluenesulfonate, p
-Toluenesulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, p-toluenesulfonic acid bis (p-tert-butoxyphenyl) phenylsulfonium, p-toluenesulfonic acid tris (p-ter)
t-butoxyphenyl) sulfonium, triphenylsulfonium nonafluorobutanesulfonate, triphenylsulfonium butanesulfonate, trimethylsulfonium trifluoromethanesulfonate, trimethylsulfonium p-toluenesulfonate, cyclohexylmethyl trifluoromethanesulfonate (2-oxocyclohexyl) Sulfonium, cyclohexylmethyl (2-oxocyclohexyl) sulfonium p-toluenesulfonate, dimethylphenylsulfonium trifluoromethanesulfonate, dimethylphenylsulfonium p-toluenesulfonate, dicyclohexylphenylsulfonium trifluoromethanesulfonate, dicyclohexylphenylsulfonium p-toluenesulfonate , Trifluoromethanesulfone Trinaphthylsulfonium, cyclohexylmethyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, (2-norbornyl) methyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, ethylenebis [methyl (2-oxocyclopentyl) sulfonium trifluoromethanesulfone Nato], onium salts such as 1,2′-naphthylcarbonylmethyltetrahydrothiophenium triflate, bis (benzenesulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, bis (xylenesulfonyl) diazomethane, bis (cyclohexylsulfonyl) Diazomethane, bis (cyclopentylsulfonyl) diazomethane, bis (n-butylsulfonyl) diazomethane, bis (isobutyl) Ruhoniru)
Diazomethane, bis (sec-butylsulfonyl) diazomethane, bis (n-propylsulfonyl) diazomethane, bis (isopropylsulfonyl) diazomethane, bis (tert-butylsulfonyl) diazomethane, bis (n-amylsulfonyl) diazomethane, bis (isoamylsulfonyl) Diazomethane, bis (sec-amylsulfonyl) diazomethane, bis (tert-amylsulfonyl) diazomethane, 1-cyclohexylsulfonyl-1- (tert-butylsulfonyl) diazomethane, 1-cyclohexylsulfonyl-1- (tert-
Diazomethane derivatives such as amylsulfonyl) diazomethane, 1-tert-amylsulfonyl-1- (tert-butylsulfonyl) diazomethane, bis-o- (p-
Toluenesulfonyl) -α-dimethylglyoxime, bis-o- (p-toluenesulfonyl) -α-diphenylglyoxime, bis-o- (p-toluenesulfonyl)
-Α-dicyclohexylglyoxime, bis-o- (p
-Toluenesulfonyl) -2,3-pentanedione glyoxime, bis-o- (p-toluenesulfonyl) -2
-Methyl-3,4-pentanedione glyoxime, bis-o- (n-butanesulfonyl) -α-dimethylglyoxime, bis-o- (n-butanesulfonyl) -α-diphenylglyoxime, bis-o- (N-butanesulfonyl) -α-dicyclohexylglyoxime, bis-o
-(N-butanesulfonyl) -2,3-pentanedione glyoxime, bis-o- (n-butanesulfonyl)-
2-Methyl-3,4-pentanedione glyoxime, bis-o- (methanesulfonyl) -α-dimethylglyoxime, bis-o- (trifluoromethanesulfonyl)-
α-dimethylglyoxime, bis-o- (1,1,1-
Trifluoroethanesulfonyl) -α-dimethylglyoxime, bis-o- (tert-butanesulfonyl)-
α-dimethylglyoxime, bis-o- (perfluorooctanesulfonyl) -α-dimethylglyoxime, bis-o- (cyclohexanesulfonyl) -α-dimethylglyoxime, bis-o- (benzenesulfonyl) -α
-Dimethylglyoxime, bis-o- (p-fluorobenzenesulfonyl) -α-dimethylglyoxime, bis-o- (p-tert-butylbenzenesulfonyl)-
glyoxime derivatives such as α-dimethylglyoxime, bis-o- (xylenesulfonyl) -α-dimethylglyoxime, bis-o- (camphorsulfonyl) -α-dimethylglyoxime, bisnaphthylsulfonylmethane,
Bissulfone derivatives such as bistrifluoromethylsulfonylmethane, bismethylsulfonylmethane, bisethylsulfonylmethane, bispropylsulfonylmethane, bisisopropylsulfonylmethane, bis-p-toluenesulfonylmethane and bisbenzenesulfonylmethane, 2
-Cyclohexylcarbonyl-2- (p-toluenesulfonyl) propane, 2-isopropylcarbonyl-2-
Β-ketosulfone derivative such as (p-toluenesulfonyl) propane, disulfone derivative such as diphenyldisulfone and dicyclohexyldisulfone, 2,6-dinitrobenzyl p-toluenesulfonate, nitro such as 2,4-dinitrobenzyl p-toluenesulfonate Benzyl sulfonate derivatives, 1,2,3-tris (methanesulfonyloxy) benzene, 1,2,3-tris (trifluoromethanesulfonyloxy) benzene, 1,2,3-tris (p-toluenesulfonyloxy) benzene, etc. Sulfonate derivative, N-hydroxysuccinimide methyl sulfonate, N-hydroxysuccinimide trifluoromethyl sulfonate, N-hydroxysuccinimide ethyl sulfonate, N-
Hydroxysuccinimide propyl sulfonate, N-hydroxysuccinimide isopropyl sulfonate, N-hydroxysuccinimide pentyl sulfonate, N-hydroxysuccinimide octyl sulfonate, N-hydroxysuccinimide-p-toluene sulfonate, N-hydroxysuccinimide -P-anisyl sulfonate,
N-hydroxysuccinimide-2-chloroethyl sulfonate, N-hydroxysuccinimide benzene sulfonate, N-hydroxysuccinimide-2,4,6-trimethylphenyl sulfonate, N-hydroxysuccinimide naphthyl sulfonate, N- Hydroxy-2-phenylsuccinimide methylsulfonic acid ester, N-hydroxymaleimidomethylsulfonic acid ester, N-hydroxymaleimidoethylsulfonic acid ester, N-hydroxy-2-phenylmaleimidomethylsulfonic acid ester, N-hydroxyglutarimidemethylsulfonic acid ester Ester, N-
Hydroxyglutarimide phenyl sulfonate, N-hydroxyphthalimide methyl sulfonate, N-hydroxyphthalimide phenyl sulfonate, N-hydroxyphthalimide trifluoromethane sulfonate, N-hydroxyphthalimide-p-toluene sulfonate, N- Hydroxy-
1,8-naphthalimidomethyl sulfonate, N
-Hydroxy-1,8-naphthalimidophenyl sulfonic acid ester, N-hydroxy-5-norbornene-
2,3-dicarboximidomethyl sulfonate, N-hydroxy-5-norbornene-2,3-dicarboximide trifluoromethane sulfonate, N-hydroxy-5-norbornene-2,3-dicarboximide-p Examples thereof include sulfonic acid ester derivatives of N-hydroxyimide compounds such as toluenesulfonic acid ester, trifluoromethanesulfonic acid triphenylsulfonium, trifluoromethanesulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, trifluoromethanesulfonic acid. Tris (p-
tert-butoxyphenyl) sulfonium, p-toluenesulfonate triphenylsulfonium, p-toluenesulfonate (p-tert-butoxyphenyl) diphenylsulfonium, p-toluenesulfonate tris (p-tert-butoxyphenyl) sulfonium, trifluoromethane Trinaphthylsulfonium sulfonate, cyclohexylmethyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, (2-norbornyl) methyl (2) trifluoromethanesulfonate
-Oxocyclohexyl) sulfonium, 1,2'-naphthylcarbonylmethyltetrahydrothiophenium triflate and other onium salts, bis (benzenesulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis ( n-butylsulfonyl) diazomethane,
Bis (isobutylsulfonyl) diazomethane, bis (s
ec-Butylsulfonyl) diazomethane, bis (n-propylsulfonyl) diazomethane, bis (isopropylsulfonyl) diazomethane, bis (tert-butylsulfonyl) diazomethane and other diazomethane derivatives, bis-o- (p-toluenesulfonyl) -α-dimethyl Glyoxime, bis-o- (n-butanesulfonyl) -α-
Glyoxime derivatives such as dimethylglyoxime, bissulfone derivatives such as bisnaphthylsulfonylmethane, N-
Hydroxysuccinimide methyl sulfonate,
N-hydroxysuccinimide trifluoromethyl sulfonate, N-hydroxysuccinimide propyl sulfonate, N-hydroxysuccinimide isopropyl sulfonate, N-hydroxysuccinimide pentyl sulfonate, N-hydroxysuccinimide p-toluene sulfonate,
N-hydroxy-1,8-naphthalimide methyl sulfonate, N-hydroxy-1,8-naphthalimide phenyl sulfonate, N-hydroxysuccinimide trifluoromethane sulfonate, etc.
A sulfonic acid ester derivative of a hydroxyimide compound is 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 rectangularity improving effect, and the diazomethane derivative and the glyoxime derivative are excellent in the standing wave reducing effect, but by combining the two, fine adjustment of the profile can be performed.

The amount of the acid generator added is preferably 0.1 to 15 parts, more preferably 0.5 to 8 parts, based on 100 parts of the base resin. If it is less than 0.1 part, the sensitivity may be poor, and if it is more than 15 parts, the resolution of the resist material may be deteriorated due to the decrease of the alkali dissolution rate, and the monomer component becomes excessive, resulting in heat resistance. There is a case where the sex is deteriorated.

The resist composition of the present invention may further contain a dissolution control agent as the component (D). The dissolution control agent has an average molecular weight of 100 to 1,000, preferably 150 to 800, and the hydrogen atom of the phenolic hydroxyl group of a compound having two or more phenolic hydroxyl groups in the molecule is entirely converted to an acid labile group. As the compound, a compound in which the hydrogen atom of the carboxyl group of the compound having a carboxyl group in the molecule is substituted with an acid labile group in the average of 80 to 100 mol% on the whole is blended.

The substitution rate of the hydrogen atom of the phenolic hydroxyl group or the carboxyl group by the acid labile group is 0 mol% or more, preferably 30 mol% or more of the whole phenolic hydroxyl group or the carboxyl group, and The upper limit is 100 mol%, more preferably 80 mol%.

In this case, the phenolic hydroxyl group is 2
As the compound having three or more or the compound having a carboxyl group, those represented by the following formulas (i) to (xiv) are preferable.

[0180]

[Chemical formula 67]

[0181]

[Chemical 68]

[0182]

[Chemical 69]

[0183]

[Chemical 70] (However, in the formula, R ¹⁵ and R ¹⁶ are each a hydrogen atom or a linear or branched alkyl group or alkenyl group having 1 to 8 carbon atoms, and R ¹⁷ is a hydrogen atom or a linear chain having 1 to 8 carbon atoms. Linear or branched alkyl group or alkenyl group, or-
(R ²¹⁾ is _h -COOH, R ¹⁸ is - (CH _{2) i} -
(I = 2 to 10), C6 to C10 arylene group, carbonyl group, sulfonyl group, oxygen atom or sulfur atom, R
¹⁹ 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 R ²⁰ is a hydrogen atom or a straight chain 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,
²¹ is a linear or branched alkylene group having 1 to 10 carbon atoms, and R ²² is a hydrogen atom or a hydroxyl group. Also, j is 0
It is an integer of 5 and u and h are 0 or 1. s, t,
s ', t', s ", and t" are s + t = 8,
It is a number that satisfies s ′ + t ′ = 5 and s ″ + t ″ = 4 and has at least one hydroxyl group in each phenyl skeleton. α is a number in which the molecular weights of the compounds of the formulas (viii) and (ix) are 100 to 1,000. )

In the above formula, R ¹⁵ and R ¹⁶ are, for example, hydrogen atom, methyl group, ethyl group, butyl group, propyl group, ethynyl group, cyclohexyl group, and R ¹⁷ are, for example, R
¹⁵ , the same as R ¹⁶ , or --COOH, --CH ₂
COOH and R ¹⁸ are, for example, ethylene group, phenylene group, carbonyl group, sulfonyl group, oxygen atom, sulfur atom and the like, and R ¹⁹ is, for example, methylene group or R ¹⁸
Examples of R ²⁰ similar to those described above 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, as the acid labile group of the dissolution control agent, the group represented by the above general formula (4) and the above general formula (5)
And a tertiary alkyl group having 4 to 20 carbon atoms, a trialkylsilyl group having 1 to 6 carbon atoms in each alkyl group, an oxoalkyl group having 4 to 20 carbon atoms, and the like.

The blending amount of the above dissolution control agent is such that the base resin 1
It is 0 to 50 parts, preferably 5 to 50 parts, and more preferably 10 to 30 parts relative to 00 parts, and they can be used alone or in combination of two or more kinds. If the content is less than 5 parts, the resolution may not be improved, and if it exceeds 50 parts, the pattern film may be reduced and the resolution may be deteriorated.

The above dissolution control agent can be synthesized by chemically reacting a compound having a phenolic hydroxyl group or a carboxyl group with an acid labile group as in the base resin.

The resist material of the present invention may be used as another dissolution control agent instead of or in addition to the above-mentioned dissolution control agent, which has a weight average molecular weight of less than 1,000 and which has a carboxyl group in the molecule. A compound in which the hydrogen atom of the group is partially substituted with an acid labile group at a rate of 0% to 100% on average as a whole can be blended.

In this case, the compound in which the hydrogen atom of the carboxyl group is partially substituted with such an acid labile group has a repeating unit represented by the following general formula (11) and has a weight average molecular weight of less than 1,000. 1 selected from certain compounds
One or more compounds are preferred.

[0190]

[Chemical 71] (In the formula, Z, Z ′, R ² , p1, p2, p3, p4,
x and z have the same meanings as above. )

Here, the acid labile group of the dissolution control agent is a group represented by the general formula (4), a group represented by the general formula (5), or a tertiary alkyl group having 4 to 20 carbon atoms. Examples of the alkyl group include a trialkylsilyl group having 1 to 6 carbon atoms and an oxoalkyl group having 4 to 20 carbon atoms.

The amount of the other dissolution control agent to be added is such that the total amount of the dissolution control agent added to the above-mentioned dissolution control agent is the base resin 10.
0 to 50 parts, especially 0 to 30 parts, preferably 0 to 0 parts
It is preferably in the range of about 5 parts.

The above-mentioned other dissolution control agent can be synthesized by chemically reacting a compound having a carboxyl group with an acid labile group as in the base resin.

Further, since the dissolution control agent (D) does not impair the oxygen plasma etching resistance, a silicone compound can be preferably used. As the dissolution control agent for the silicone compound, the carboxyl group or the hydroxyl group of the silicone compound represented by the following general formulas (12) to (14) can be used as te.
It is preferable to use those protected with an rt-butyl group or a tert-butoxycarbonylmethyl group.

[0195]

[Chemical 72] (In the formula, R ¹⁰ represents a methyl group or a phenyl group, R ¹¹ represents a carboxyethyl group or a p-hydroxyphenylalkyl group (wherein the alkyl group is a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms). E) is a trimethylsilyl group, a triphenylsilyl group or -SiR ¹⁰ R
¹¹ (R ¹⁰ and R ¹¹ have the same meanings as described above).
γ is an integer of 0 to 50, δ is an integer of 1 to 50, and ε is 3-1.
Indicates an integer of 0. )

Here, as the silicone compounds obtained by protecting the carboxyl group or hydroxyl group of the silicone compounds of the above formulas (12) to (14) with an alkali-soluble group (tert-butyl group or tert-butoxycarbonylmethyl group), The compounds of the following A to C groups are exemplified. In addition, Me represents a methyl group and t-Bu represents a tert-butyl group.

[0197]

[Chemical formula 73]

[0198]

[Chemical 74]

[0199]

[Chemical 75]

The content of the dissolution control agent was 4 based on the total amount of the base resin.
It is preferably 0% by weight or less, and particularly preferably 10 to 30% by weight. If it is more than 40% by weight, the oxygen plasma etching resistance of the resist film is remarkably lowered, and there is a possibility that it cannot be used as a two-layer resist.

Further, the resist material of the present invention comprises (E)
A basic compound can be added as a component.

The basic compound to be added as the (E) additive is preferably a compound capable of suppressing the diffusion rate when the acid generated from the acid generator diffuses in the resist film. With the addition of a basic compound, the acid diffusion rate in the resist film is suppressed to improve the resolution, the sensitivity change after exposure is suppressed, and the dependency on the substrate and the environment is reduced, and the exposure margin and pattern are reduced. The profile etc. can be improved.

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

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

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

Further, examples of the nitrogen-containing compound having a carboxy group include aminobenzoic acid, indolecarboxylic acid, amino acid derivatives (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, and 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-indole methanol 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, piperidine ethanol, 1- (2-hydroxyethyl) pyrrolidine,
1- (2-hydroxyethyl) -2-pyrrolidinone, 3
-Piperidino-1,2-propanediol, 3-pyrrolidino-1,2-propanediol, 8-hydroxyjulolidine, 3-cuinclidinol, 3-tropanol,
1-Methyl-2-pyrrolidine ethanol, 1-aziridine ethanol, N- (2-hydroxyethyl) phthalimide, N- (2-hydroxyethyl) isonicotinamide and the like are exemplified. Examples of the amide derivative include formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N,
Examples include N-dimethylacetamide, propionamide, benzamide and the like. Examples of the imide derivative include phthalimide, succinimide, and maleimide.

Further, basic compounds represented by the following general formulas (15) and (16) can be blended.

[0208]

[Chemical 76] (In the formula, R⁴¹, R⁴², R⁴³, R⁴⁷, R⁴⁸Are independent
A linear, branched or cyclic C1-C20 al
Xylene group, R⁴⁴, R⁴⁵, R⁴⁶, R⁴⁹, R⁵⁰Is a hydrogen atom,
Represents an alkyl group or an amino group having 1 to 20 carbon atoms, R⁴⁴
And R⁴⁵, R⁴⁵And R ⁴⁶, R⁴⁴And R⁴⁶, R⁴⁴And R⁴⁵And R⁴⁶,
R⁴⁹And R⁵⁰May be bonded to each other to form a ring.
S, T, and U each represent an integer of 0 to 20. However,
When S, T, U = 0, R⁴⁴, R⁴⁵, R⁴⁶, R⁴⁹, R⁵⁰
Does not include a hydrogen atom. )

Here, the alkylene group of R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁷ and R ⁴⁸ has 1 to 20 carbon atoms, preferably 1 carbon atom.
10 to 10, more preferably 1 to 8, specifically, methylene group, ethylene group, n-propylene group, isopropylene group, n-butylene group, isobutylene group, n-
Examples thereof 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 represented by R ⁴⁴ , R ⁴⁵ , R ⁴⁶ , R ⁴⁹ and R ⁵⁰ has 1 to 20 carbon atoms, preferably 1 to 20 carbon atoms.
8 and more preferably 1 to 6, which may be linear, branched or cyclic. Specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, hexyl group, nonyl group, decyl group, dodecyl group. Group, tridecyl group, cyclopentyl group, cyclohexyl group and the like.

Further, R ⁴⁴ and R ⁴⁵ , R ⁴⁵ and R ⁴⁶ , R ⁴⁴ and R
^When R ⁴⁶ , R ⁴⁴ and R ⁴⁵ and R ⁴⁶ , and R ⁴⁹ and R ⁵⁰ form a ring, R ⁴⁴ , R ⁴⁵ , R ⁴⁶ , R ⁴⁹ , and R ⁵⁰ each have 1 to 20 carbon atoms, more preferably 1 carbon atom. ~ 8, more preferably 1 ~
6 are alkylene groups, and these rings have 1 to 1 carbon atoms.
6, especially 1 to 4 alkyl groups may be branched.

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

Specific examples of the compounds (15) and (16) 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) ethoxy} ethyl] amine, 4,
7,13,16,21,24-hexaoxa-1,10
-Diazabicyclo [8.8.8] hexacosane, 4,
7,13,18-Tetraoxa-1,10-diazabicyclo [8.5.5] eicosane, 1,4,10,13-
Tetraoxa-7,16-diazabicyclooctadecane, 1-aza-12-crown-4,1-aza-15-
Crown-5, 1-aza-18-crown-6 and the like can be mentioned. Especially tertiary amine, aniline derivative, pyrrolidine derivative, pyridine derivative, quinoline derivative, amino acid derivative, nitrogen-containing compound having a hydroxy group, nitrogen-containing compound having a hydroxyphenyl group, alcoholic nitrogen-containing compound, amide derivative, imide derivative, Tris {2-
(Methoxymethoxy) ethyl} amine, tris {(2-
(2-Methoxyethoxy) ethyl} amine, tris [2
-{(2-methoxyethoxy) methyl} ethyl] amine, 1-aza-15-crown-5 and the like are preferable.

The amount of the above-mentioned basic compound to be added is such that the acid generator 1
0.001-10 parts, preferably 0.01-
It is one copy. If the blending amount is less than 0.001 part, the effect as an additive may not be sufficiently obtained, and if it exceeds 10 parts, the resolution and sensitivity may decrease.

Further, the resist material of the present invention comprises (F)
As a component, a compound having a group represented by ≡C—COOH in the molecule can be blended.

In the molecule blended as the component (F)
The compound having a group represented by ≡C-COOH is, for example,
One or more compounds selected from the following group I and group II
Compounds can be used, but are not limited to these
Not of. By blending component (F), PE for resist
D stability is improved, and edge roughness on the nitride film substrate
Can be improved. [Group I] Compounds represented by the following general formulas (17) to (26)
Some or all of the hydrogen atoms of the phenolic hydroxyl group of the product-
R⁵¹ -COOH (R⁵¹ Is a straight or branched chain having 1 to 10 carbon atoms
In the molecule and
Of phenolic hydroxyl group (C) and ≡C-COOH of
The molar ratio with the group (D) is C / (C + D) = 0.1
A compound that is 1.0. [Group II] Compounds represented by the following general formulas (27) to (31)
Compound

[0217]

[Chemical 77]

[0218]

[Chemical 78] (However, in the formula, R ¹ is a hydrogen atom or a methyl group,
R ⁵² and R ⁵³ are each a hydrogen atom or a linear or branched alkyl group or alkenyl group having 1 to 8 carbon atoms,
⁵⁴ is a hydrogen atom or a linear or branched alkyl or alkenyl group having 1 to 8 carbon atoms, or - (R ⁵⁹⁾ _h -CO
OR 'group (R' is a hydrogen atom or -R ⁵⁹ -COOH) is, R ⁵⁵ is _{- (CH 2) i - (} i = 2~10), a carbon number 6
10 arylene group, carbonyl group, sulfonyl group,
An oxygen atom or a sulfur atom, R ⁵⁶ 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 R ⁵⁷ is a hydrogen atom or 1 to 8 carbon atoms. Is a linear or branched alkyl group, an alkenyl group, a phenyl group or a naphthyl group each substituted with a hydroxyl group, and R ⁵⁸ is a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms, or an alkenyl group or -R ⁵⁹ -COOH group. R ⁵⁹ has 1 to 1 carbon atoms
0 is a linear or branched alkylene group. j is 0
It is an integer of 5 and u and h are 0 or 1. s1, t
1, s2, t2, s3, t3, s4, and t4 are s
1 + t1 = 8, s2 + t2 = 5, s3 + t3 = 4, s4
It is a number that satisfies + t4 = 6 and has at least one hydroxyl group in each phenyl skeleton. κ is the formula (2
The compound of 3) has a weight average molecular weight of 1,000 to 5,000.
And λ is the number that gives the compound of formula (24) a weight average molecular weight of 1,000 to 10,000. )

[0219]

[Chemical 79] (R ⁵² , R ⁵³ and R ⁵⁹ have the same meanings as described above. S5,
t5 is a number that satisfies s5 ≧ 0 and t5 ≧ 0 and satisfies s5 + t5 = 5. R ⁶⁰ is a hydrogen atom or a hydroxyl group, h ′
Is 0 or 1. )

Specific examples of the component (F) include compounds represented by the following general formulas VIII-1 to 14 and IX-1 to 10, but not limited thereto.

[0221]

[Chemical 80]

[0222]

[Chemical 81]

[0223]

[Chemical formula 82] (However, R "represents a hydrogen atom or a CH ₂ COOH group,
In each compound, 10 to 100 mol% of R "is CH ₂ C
It is an OOH group. α and κ have the same meanings as above. )

[0224]

[Chemical 83]

[0225]

[Chemical 84]

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

The addition amount of the compound having a group represented by ≡C-COOH in the molecule is 0 to 5 parts, preferably 0.1 to 5 parts, and more preferably 0.1 to 100 parts of the base resin. -3 parts, more preferably 0.1-2 parts. 5
If it is larger than the area, the resolution of the resist material may decrease.

Further, the resist material of the present invention comprises (G)
An acetylene alcohol derivative can be added as a component, which can improve the storage stability.

As the acetylene alcohol derivative, those represented by the following general formulas (32) and (33) can be preferably used.

[0230]

[Chemical 85] (In the formula, 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. )

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

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

In addition, in the present invention, the above (A) to
As a resist material different from the resist material containing the component (G), in addition to (A) the above-mentioned organic solvent, (B) the above-mentioned polymer silicone compound, and (C) the above-mentioned acid generator,
Provided is a resist material containing a compound (H) which is crosslinked by the action of the following acid.

Examples of the compound (H) which is crosslinked by the action of an acid include the following epoxy compounds and urea compounds.

[0235]

[Chemical 86]

The compounding amount of the compound which is crosslinked by the action of an acid is preferably 5 to 95 relative to 100 parts of the base resin.
Parts, particularly preferably 15 to 85 parts, more preferably 20 parts.
~ 75 parts. If it is less than 5 parts, it is difficult to cause a sufficient crosslinking reaction, and the film remaining rate is lowered, and the pattern is meandered or swollen. Further, if the amount exceeds 95 parts, there is a large amount of scum and the developability tends to deteriorate.

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

Here, the surfactant is preferably a nonionic one, such as perfluoroalkyl polyoxyethylene ethanol, fluorinated alkyl ester, perfluoroalkylamine oxide, perfluoroalkyl EO adduct, fluorine-containing organosiloxane system. A compound etc. are mentioned. For example, Florard "FC-430",
"FC-431" (both are Sumitomo 3M Limited)
Manufactured by Asahi Glass Co., Ltd., Unidyne "DS-40", Surflon "S-141", "S-145"
1 "," DS-403 "," DS-451 "(all manufactured by Daikin Industries, Ltd.), Megafac" F-815 "
1 "(manufactured by Dainippon Ink Industry Co., Ltd.)," X-70-09 "
2 "," X-70-093 "(all manufactured by Shin-Etsu Chemical Co., Ltd.) and the like. Preferably, Florard "FC-430" (manufactured by Sumitomo 3M Limited),
"X-70-093" (made by Shin-Etsu Chemical Co., Ltd.) is mentioned.

A pattern can be formed by using the resist material of the present invention by adopting a known lithography technique. For example, a film such as a silicon wafer can be formed to a film thickness of 0 by a method such as spin coating. 0.5-2.0μ
m so that it becomes 60 m on a hot plate.
~ 150 ° C, 1 to 10 minutes, preferably 80 to 120
Prebak at 1 ° C for 1 to 5 minutes. Next, a mask for forming a desired pattern is held over the resist film, and a high-energy ray such as deep ultraviolet rays having a wavelength of 300 nm or less, excimer laser, or X-ray, or an electron beam is exposed at an exposure dose of 1
~200mJ / cm ^2, preferably about 10~100m
After irradiating so as to be about J / cm ² , it is 60 to 150 ° C. on a hot plate for 1 to 5 minutes, preferably 80 to
Post exposure bake (P
EB) Furthermore, 0.1-5%, preferably 2-3%
Tetramethylammonium hydroxide (TMA
H) or the like using an alkaline aqueous solution for 0.1 to 3 minutes, preferably 0.5 to 2 minutes, by a conventional method such as a dipping method, a paddle method, or a spray method. By developing, a target pattern is formed on the substrate. The material of the present invention is particularly suitable for fine patterning by deep ultraviolet rays having a wavelength of 254 to 193 nm or excimer laser, X-rays and electron beams among high energy rays. If the above range falls outside the upper and lower limits, the desired pattern may not be obtained.

Since the resist material of the present invention has a high molecular silicone compound as a base resin and is excellent in oxygen plasma etching resistance, it is also useful as a two-layer resist material.

That is, according to a conventional method, a thick organic polymer layer is formed as a lower layer resist on a substrate, and then 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.

As the lower layer resist, a novolac resin type positive type resist can be used. After being coated on the substrate, it is hard baked at 200 ° C. for 1 hour to prevent intermixing with the silicone type resist. be able to.

[0243]

EFFECTS OF THE INVENTION The resist material using the polymeric silicone compound of the present invention as a base resin is sensitive to high energy rays, and is excellent in sensitivity and resolution, and is therefore useful for fine processing by electron beams or deep ultraviolet rays. is there. In particular, since the absorption at the exposure wavelength of the ArF excimer laser and the KrF excimer laser is small, it has a feature that a fine pattern can be easily formed perpendicular to the substrate. Further, since the oxygen plasma etching resistance is excellent, the two-layer resist in which the resist film of the present invention is applied on the lower resist film has a feature that a fine pattern can be formed with a high aspect ratio.

[0244]

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

[Synthesis Example 1] Synthesis of poly (3-carboxycyclohexylsilsesquioxane) 150.0 g (0.544 mol) of 3-trichlorosilyl-1-cyclohexylcarboxylic acid methyl ester was dissolved in 150 g of toluene, and 300 g of water was added. It was added dropwise into it with stirring at room temperature. After completion of the dropping, the acidic aqueous layer was separated from the reaction mixture, and then the organic layer was washed with 1 L of water, and further washed twice with water after the aqueous layer became neutral. The solvent of the organic layer was distilled off by an evaporator. The concentrate is 200 ℃
It was heated for 2 hours and polymerized. A solution obtained by adding 800 g of tetrahydrofuran to the polymer and dissolving it was added dropwise to 1,000 g of a 10% sodium hydroxide solution, and heated at 40 ° C. for 3 hours to hydrolyze the methyl ester group. The polymer was crystallized by acidifying with hydrochloric acid, filtered and dried to obtain poly (3-carboxycyclohexylsilsesquioxane) in a yield of 8
Obtained in 3.4 g. The weight average molecular weight of the obtained polymer was 3,000.

[Synthesis Example 2] Synthesis of poly [(3-carboxycyclohexylsilsesquioxane)-(cyclohexylsilsesquioxane)] 3-trichlorosilyl-1-cyclohexylcarboxylic acid methyl ester 75.0 g (0.272 mol) ) And cyclohexyltrichlorosilane 59.2 g (0.272 m
ol) was dissolved in 150 g of toluene and added dropwise to 300 g of water while stirring at room temperature. After completion of the dropping, the acidic aqueous layer was separated from the reaction mixture, and then the organic layer was washed with 1 L of water, and further washed twice with water after the aqueous layer became neutral. The solvent of the organic layer was distilled off by an evaporator. The concentrate was heated at 200 ° C. for 2 hours to polymerize. 10% of a polymer obtained by adding 800 g of tetrahydrofuran to a polymer and dissolving it.
It was added dropwise to 1,000 g of sodium hydroxide solution and heated at 40 ° C. for 3 hours to hydrolyze the methyl ester group. The polymer was crystallized by acidification with hydrochloric acid, filtered and dried to obtain poly [(3-carboxycyclohexylsilsesquioxane)-(cyclohexylsilsesquioxane)] in a yield of 82.0 g. The weight average molecular weight of the obtained polymer was 3,500. In the ¹ H-NMR analysis, the composition ratio of 3-carboxycyclohexylsilsesquioxane / cyclohexylsilsesquioxane was 50.
It was / 50 (molar ratio).

[Synthesis Examples 3 to 8] Silicone polymers shown in Table 1 were obtained in the same manner as in Synthesis Examples 1 and 2. The weight average molecular weights and ratios of the polymers obtained in the above Synthesis Examples 1 to 8 are shown in Table 1.
Shown in.

[0248]

[Chemical 87]

[0249]

[Chemical 88]

[0250]

[Table 1]

[Synthesis Example 9] 50 g of the polymer obtained in Synthesis Example 1 was dissolved in 450 ml of tetrahydrofuran, and after adding a catalytic amount of p-toluenesulfonic acid, 15.0 g of ethyl vinyl ether was added with stirring at 20 ° C. .
After reacting for 1 hour, the mixture was neutralized with concentrated aqueous ammonia, and the neutralization reaction solution was added dropwise to 5 L of water to obtain a white solid. This was filtered, dissolved in 100 ml of acetone, added dropwise to 5 L of water, filtered, and vacuum dried. Dissolve 60 g of the obtained polymer in 560 ml of tetrahydrofuran,
After adding 34.0 g of 1-hydrobenzotriazole and 31.6 g of diisopropyl carboxylic diimide, 7.7 g of ethanolamine was added. After reacting at 30 ° C. for 5 hours, the mixture was concentrated and added dropwise to 3 L of water to obtain a white solid. This was filtered, dissolved in 50 ml of acetone, added dropwise to 3 L of water, filtered, and vacuum dried to obtain a polymer. The obtained polymer has the following rational formula (Polym.
Has a structure represented by 1), the analysis by ¹ H-NMR, 5 of the hydrogen atoms of the carboxyl groups of the polymer compound
0% is ethoxyethylated, is 50% -NHCH ₂ C
It was confirmed that it was replaced with H ₂ OH.

[Synthesis Example 10] 50 g of the polymer obtained in Synthesis Example 1 was dissolved in 450 ml of tetrahydrofuran,
After adding a catalytic amount of p-toluenesulfonic acid, ethylene 1-propenyl ether 12.0 with stirring at 20 ° C.
g, and after 2 hours, 8.7 g of 1,4-butanediol divinyl ether was added dropwise, and after reacting for 30 minutes,
The solution was neutralized with concentrated aqueous ammonia and the neutralization reaction solution was added dropwise to 5 L of water to obtain a white solid. This was filtered, dissolved in 100 ml of acetone, added dropwise to 5 L of water, filtered, and vacuum dried. 60 g of the obtained polymer was dissolved in 560 ml of tetrahydrofuran, 34.0 g of 1-hydrobenzotriazole and 31.6 g of diisopropyl carboxylic diimide were added, and then 2-amino-2-methyl-1,
26.3 g of 3-propanediol was added. After reacting at 30 ° C. for 5 hours, the mixture was concentrated and added dropwise to 3 L of water to obtain a white solid. After filtering this, acetone 50
It was dissolved in ml, dropped into 3 L of water, filtered, and vacuum dried to obtain a polymer. The obtained polymer has a structure represented by the following rational formula (Polym.2), and has a structure of ¹ H-NM
In the analysis by R, 40% of the hydrogen atoms of the carboxyl group of the polymer compound were ethoxypropylated and 20%
Has a crosslinked structure, and 40% is NHC (CH ₃ ) (CH ₂ O
It was confirmed that it was replaced with H) ₂ .

[Synthesis Examples 11 to 18] In Synthesis Examples 9 and 10, the polymer of any of Synthesis Examples 1 to 8 was used, and Po was used instead of ethyl vinyl ether and ethanolamine.
lym. Acid labile groups represented by 3 to 10 and the general formula (2b)
By using the same method as in the following formula (1) except that a compound capable of introducing a group represented by is used and 1,4-bis [(vinyloxy) methyl] cyclohexane is used instead of 1,4-butanediol divinyl ether. Pol
ym. The silicone polymer shown by 3-10) was obtained.

[Synthesis Example 19] 50 g of the polymer obtained in Synthesis Example 1 was dissolved in 450 ml of tetrahydrofuran,
After adding 69.7 g of trifluoroacetic anhydride, 17.2 g of t-butyl alcohol was added with stirring at 20 ° C. After reacting for 5 hours, the mixture was neutralized with concentrated aqueous ammonia, and the neutralization reaction solution was added dropwise to 5 L of water to obtain a white solid. This was filtered, dissolved in 100 ml of acetone, added dropwise to 5 L of water, filtered, and vacuum dried. 60 g of the obtained polymer was dissolved in 560 ml of tetrahydrofuran, 34.0 g of 1-hydrobenzotriazole and 31.6 g of diisopropyl carboxylic diimide were added, and then 4-
19.5 g of aminomethyl-1-cyclohexanol was added. After reacting at 30 ° C. for 5 hours, the mixture was concentrated and washed with water 3
When added dropwise to L, a white solid was obtained. This was filtered, dissolved in 50 ml of acetone, added dropwise to 3 L of water, filtered, and vacuum dried to obtain a polymer. The obtained polymer has a structure represented by the following rational formula (Polym.11), and in the analysis by ¹ H-NMR, 40% of the hydrogen atoms of the carboxyl group of the polymer compound were tert-butylated, It was confirmed that 60% was replaced by the following formula.

[0255]

[Chemical 89]

[Synthesis Example 20] The same method as in Synthesis Example 19 except that the polymer of Synthesis Example 2 was used and 3-amino-1,2-propanediol was used instead of 4-aminomethyl-1-cyclohexanol. To obtain a silicone polymer represented by the following rational formula (Polym.12).

[Synthesis Example 21] By the same method as in Synthesis Example 19 except that the polymer of Synthesis Example 6 was used and 2- (2-aminoethoxy) ethanol was used instead of 1-aminomethyl-1-cyclohexanol. A silicone polymer represented by the following rational formula (Polym.13) was obtained.

[Synthesis Example 22] 50 g of the polymer obtained in Synthesis Example 1 was dissolved in 450 ml of tetrahydrofuran,
After adding a catalytic amount of p-toluenesulfonic acid, 21.5 g of ethyl-1-propenyl ether with stirring at 20 ° C.
Was added. After reacting for 2 hours, the mixture was neutralized with concentrated aqueous ammonia, and the neutralization reaction solution was added dropwise to 5 L of water to obtain a white solid. This was filtered, dissolved in 100 ml of acetone, added dropwise to 5 L of water, filtered, and vacuum dried. Dissolve 60 g of the obtained polymer in tetrahydrofuran, add potassium carbonate as a solid, and add 27.8 g of bromine ethanol while stirring, and after reacting at 60 ° C. for 6 hours, solid potassium carbonate was added from the reaction solution. Was filtered off. The solvent and unreacted bromoethanol were distilled off from the filtrate under reduced pressure. When the residue was dissolved in acetone and added dropwise to 5 L of water, a white solid was obtained. This was filtered, dissolved in 200 ml of acetone, added dropwise to 3 L of water, filtered, and vacuum dried to obtain a polymer. The obtained polymer has a structure represented by the following rational formula (Polym.14),
In analysis by ¹ H-NMR, 60% of the hydrogen atoms of the carboxyl groups of the polymer compound is ethoxypropylated, 40% that is substituted with -OCH ₂ CH ₂ OH was confirmed.

[Synthesis Example 23] The same procedure as in Synthesis Example 20 was repeated except that the polymer of Synthesis Example 6 was used, to obtain a silicone polymer represented by the following formula (Polym.15).

[0260]

[Chemical 90]

[0261]

[Chemical Formula 91]

[0262]

[Chemical Formula 92]

[0263]

[Chemical formula 93]

[0264]

[Chemical 94]

[0265]

[Chemical 95]

[Synthesis Example 24] of poly [(3-carboxycyclohexylsilsesquioxane)-(8-hydroxy-4-tricyclo [5,2,1,0 ^2,6 ] decanylsilsesquioxane)] Synthetic 3-trichlorosilyl-1-cyclohexylcarboxylic acid methyl ester 75.0 g (0.272 mol) and 8-
Acetoxy-4-trichlorosilyltricyclo [5,5
2,1,0 ^2,6 ] decane 89.1 g (0.272 mo
1) was dissolved in 150 g of toluene and added dropwise to 300 g of water with stirring at room temperature. After completion of the dropping, the acidic aqueous layer was separated from the reaction mixture, and then the organic layer was washed with 1 L of water, and further washed twice with water after the aqueous layer became neutral. The solvent of the organic layer was distilled off by an evaporator. The concentrate was heated at 200 ° C. for 2 hours to polymerize. 10% of a polymer obtained by adding 800 g of tetrahydrofuran to a polymer and dissolving it.
It was added dropwise to 1,000 g of a sodium hydroxide solution and heated at 40 ° C. for 3 hours to hydrolyze the methyl ester group and acetoxy group. Acidify with hydrochloric acid to crystallize the polymer, filter,
After drying, poly [(3-carboxycyclohexylsilsesquioxane)-(8-hydroxy-4-tricyclo [5,2,1,0 ^2,6 ] decanylsilsesquioxane] was obtained in a yield of 98.6 g. The polymer obtained had a weight average molecular weight of 4,000 and ¹ H-NMR.
In the analysis of 3-carboxycyclohexylsilsesquioxane / 8-hydroxy-4-tricyclo [5,
The composition ratio of 2,1,0 ^2,6 ] decanylsilsesquioxane was 50/50 (molar ratio).

[Synthesis Example 25] Poly [(3-carboxycyclohexylsilsesquioxane)-(8-hydroxy-4-tricyclo [5,2,1,0 ^2,6 ] decanylsilsesquioxane)-( Cyclohexylsilsesquioxane)] 3-trichlorosilyl-1-cyclohexylcarboxylic acid methyl ester 60.1 g (0.218 mol) and 8-
Acetoxy-4-trichlorosilyltricyclo [5,5
2,1,0 ^2,6 ] decane 71.4 g (0.218 mo
l) and cyclohexyltrichlorosilane 23.7 g
(0.109 mol) was dissolved in 150 g of toluene and added dropwise to 300 g of water with stirring at room temperature. After the dropping was completed, the acidic aqueous layer was separated from the reaction mixture, and then 1 L of water was added.
The organic layer was washed with water and washed with water twice more after the water layer became neutral. The solvent of the organic layer was distilled off by an evaporator. The concentrate was heated at 200 ° C. for 2 hours to polymerize.
A solution obtained by adding 800 g of tetrahydrofuran to the polymer and dissolving it was added dropwise to 1,000 g of a 10% sodium hydroxide solution and heated at 40 ° C. for 3 hours to hydrolyze the methyl ester group and the acetoxy group. The polymer was crystallized by acidification with hydrochloric acid, filtered and dried to give poly [(3-carboxycyclohexylsilsesquioxane)-(8-hydroxy-4-tricyclo [5,2,1,0 ^2,6 ]] Cyanylsilsesquioxane)-(cyclohexylsilsesquioxane)] was obtained in a yield of 83.4 g. The weight average molecular weight of the obtained polymer was 5,000. Also, ¹ H-NM
In R analysis, 3-carboxy-cyclohexyl silsesquioxane / 8-hydroxy-4-tricyclo [5,2,1,0 ^2,6] dec crab silsesquioxane /
The composition ratio of cyclohexylsilsesquioxane is 40/4
It was 0/20 (molar ratio).

[Synthesis Examples 26 to 31] Silicone polymers shown in Table 2 were obtained in the same manner as in Synthesis Examples 24 and 25. Table 2 shows the weight average molecular weight and composition ratio of the obtained polymer.

[0269]

[Table 2]

[0270]

[Chemical 96]

[0271]

[Chemical 97]

[Synthesis Example 32] 50 g of the polymer obtained in Synthesis Example 24 was dissolved in 450 ml of tetrahydrofuran, a catalytic amount of p-toluenesulfonic acid was added, and the mixture was heated at 20 ° C.
10.8 g of ethyl vinyl ether was added with stirring. After reacting for 1 hour, the mixture was neutralized with concentrated aqueous ammonia, and the neutralization reaction solution was added dropwise to 5 L of water to obtain a white solid. This was filtered, dissolved in 100 ml of acetone, added dropwise to 5 L of water, filtered, and vacuum dried. The obtained polymer had a structure represented by the following rational formula (Polym.16), and 90% of the hydrogen atoms of the carboxyl group of the polymer compound were ethoxyethylated by ¹ H-NMR analysis. Was confirmed.

[Synthesis Example 33] 50 g of the polymer obtained in Synthesis Example 31 was dissolved in 450 ml of tetrahydrofuran, a catalytic amount of p-toluenesulfonic acid was added, and the mixture was heated at 20 ° C.
8.7 g of ethyl vinyl ether was added with stirring. After reacting for 1 hour, the mixture was neutralized with concentrated aqueous ammonia, and the neutralization reaction solution was added dropwise to 5 L of water to obtain a white solid. This was filtered, dissolved in 100 ml of acetone, added dropwise to 5 L of water, filtered, and vacuum dried. 60 g of the obtained polymer was dissolved in 540 ml of tetrahydrofuran to give 27.0 g of 1-hydroxybenzotriazole,
After adding 12.6 g of N, N'-diisopropylcarbodiimide, 6.1 g of ethanolamine was added. 30 ° C
After reacting for 5 hours, the mixture was concentrated and added dropwise to 3 L of water to obtain a white solid. After filtering this, acetone 5
It was dissolved in 0 ml, added dropwise to 3 L of water, filtered, and vacuum dried to obtain a polymer. The obtained polymer has a structure represented by the following rational formula (Polym.17), and is ¹ H—N
In the analysis by MR, 60% of the hydrogen atoms of the carboxyl group of the polymer compound were ethoxyethylated, and 30%
There it was confirmed substituted with -NHCH ₂ CH ₂ OH.

[Synthesis Example 34] 50 g of the polymer obtained in Synthesis Example 31 was dissolved in 450 ml of tetrahydrofuran, a catalytic amount of p-toluenesulfonic acid was added, and the temperature was changed to 20 ° C.
Ethylene-1-propenyl ether while stirring at 6.
When 9 g was added dropwise and 2 hours later, 5.7 g of 1,4-butanediol divinyl ether was added dropwise, the mixture was reacted for 30 minutes, neutralized with concentrated aqueous ammonia, and the neutralization reaction solution was added dropwise to 5 L of water. , A white solid was obtained. After filtering this, it was dissolved in 100 ml of acetone and added dropwise to 5 L of water.
After filtration, it was vacuum dried. 60 g of the obtained polymer was dissolved in 540 ml of tetrahydrofuran, and after adding 27.0 g of 1-hydroxybenzotriazole and 12.6 g of N, N'-diisopropylcarbodiimide, 2-amino-
10.5 g of 2-methyl-1,3-propanediol was added. After reacting at 30 ° C. for 5 hours, the mixture was concentrated and washed with water 3
When added dropwise to L, a white solid was obtained. This was filtered, dissolved in 50 ml of acetone, added dropwise to 3 L of water, filtered, and vacuum dried to obtain a polymer. The obtained polymer has a structure represented by the following rational formula (Polym.18), and in the analysis by ¹ H-NMR, 40% of the hydrogen atoms of the carboxyl group of the polymer compound were ethoxypropylated, % Has a cross-linked structure, 30% is NHC
It was confirmed to be substituted with (CH ₃ ) (CH ₂ OH) ₂ .

[Synthesis Examples 35 to 41] Synthesis Examples 32 and 33,
34, the polymer of any of Synthesis Examples 24-31 was used, instead of ethyl vinyl ether and ethanolamine, Polym. In addition to the compounds capable of introducing the acid labile group shown in 19 to 25 and the group represented by the general formula (2a) or (2b), 1,4-bis [diphenyl ether is used instead of 1,4-butanediol divinyl ether. A silicone polymer represented by the following rational formula (Polym. 19 to 25) was obtained by the same method except that (vinyloxy) methyl] cyclohexane was used.

[Synthesis Example 42] 20 g of the polymer obtained in Synthesis Example 24 was dissolved in 200 ml of dimethylformamide, potassium carbonate was added as a solid, and 15.1 g of chloroacetic acid-tert-butyl ester was added with stirring. After reacting at 60 ° C. for 6 hours, solid potassium carbonate was filtered off from the reaction solution and 10 L of water was added dropwise to obtain a white solid. This was filtered, dissolved in 100 ml of acetone, added dropwise to 5 L of water, filtered, and vacuum dried to obtain a polymer. The obtained polymer has the following rational formula (Pol
ym. 26), the tert-butoxycarbonylmethylation ratio of the hydrogen atom of the carboxyl group of the polymer compound is 60 in the ¹ H-NMR analysis.
% Was confirmed.

[Synthesis Example 43] 50 g of the polymer obtained in Synthesis Example 24 was dissolved in 180 ml of tetrahydrofuran, 52.5 g of trifluoroacetic anhydride was added, and 18.5 g of t-butyl alcohol was added while stirring at 5 ° C or lower. Was added. After reacting for 2 hours, the mixture was neutralized with concentrated aqueous ammonia, and the neutralization reaction solution was added dropwise to 5 L of water to obtain a white solid. This was filtered, dissolved in 100 ml of acetone, added dropwise to 5 L of water, filtered, and vacuum dried. The obtained polymer had a structure represented by the following rational formula (Polym.27), and in the analysis by ¹ H-NMR, 80% of the hydrogen atoms of the carboxyl group of the polymer compound were te.
It was confirmed that it was rt-butylated.

[0278]

[Chemical 98]

[0279]

[Chemical 99]

[0280]

[Chemical 100]

[0281]

[Chemical 101]

[0282]

[Chemical 102]

[0283]

[Chemical 103]

[0284]

[Chemical 104]

[ Reference Examples 1 to 28] The polymers (Polym. 1 to 1) obtained in the above synthesis examples.
5) is used as a base resin, and the following formula (PAG.
5), an acid generator represented by the following formula (DRR. 1, 2), a dissolution controlling agent represented by the following formula (DRR. 1, 2), a basic compound, a formula (ACC.
The aromatic compound having a group represented by ≡C-COOH in the molecule represented by 1) is prepared in the composition shown in Tables 3 and 4 with propylene glycol monoethyl acetate (PGMEA), ethyl lactate (EL) or diethylene glycol monomethyl ether (DGLYME). ) To prepare a resist material, and each composition was filtered through a 0.2 μm Teflon filter to prepare a resist solution.

The obtained resist solution was spin-coated on a silicon wafer and applied to a thickness of 0.3 μm. Then, the silicon wafer was baked at 100 ° C. for 90 seconds using a hot plate. ArF excimer laser stepper (Nikon, NA = 0.5)
5) was used for exposure, followed by baking at 110 ° C. for 90 seconds and development with an aqueous solution of 2.38 wt% tetramethylammonium hydroxide, whereby a pattern could be obtained. The obtained resist pattern was evaluated as follows. The results are shown in Tables 3 and 4. Evaluation method: First, the sensitivity was obtained. Next, the exposure amount for resolving a 0.20 μm line and space at a ratio of 1: 1 was taken as the optimum exposure amount (Eop), and the minimum line width of the separated line and space in this exposure amount was taken as the resolution of the evaluation resist. . The shape of the resolved resist pattern was observed using a scanning electron microscope. In addition, 0.18 μm line-and-space unevenness (edge roughness) was measured with a scanning electron microscope with a length measuring function (Hitachi, S7280).

From the results shown in Tables 3 and 4, it was confirmed that these resist materials had a pattern having high resolution and no unevenness (small edge roughness).

[0288]

[Chemical 105]

[0289]

[Chemical formula 106]

[0290]

[Chemical formula 107]

[0291]

[Table 3]

[0292]

[Table 4]

[ Reference Example 29] OFPR was used as a lower layer resist material on a silicon wafer.
Apply 800 (manufactured by Tokyo Ohka Co., Ltd.) to a thickness of 2.0 μm,
It was heated at 200 ° C. for 5 minutes to be cured. The resist material used in Reference Example 1 was applied onto the lower resist film in the same manner as described above to a thickness of about 0.35 μm, and prebaked. Then perform KrF excimer laser exposure and development,
A pattern was formed on the lower resist film. At this time, a pattern perpendicular to the lower resist film can be obtained,
No expression of tailing was observed.

After that, etching was carried out 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 /
The resist film has a thickness of 15 nm / mi
It was n or less. By etching for 15 minutes, the lower resist film which was not covered with the present resist film completely disappeared, and a two-layer resist pattern having a thickness of 1 μm or more could be 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

[Examples 1 to 5, Reference Examples 30 to 59 ] The polymers (Polym. 16 to 2) obtained in the above synthesis examples.
8) is used as a base resin and the following formula (PAG.1
8), an acid generator represented by the following formula (DRR.1 to 4), a dissolution controlling agent represented by the following formula (DRR.
1) a compound having a group represented by ≡C—COOH in the molecule, a compound capable of crosslinking by the action of an acid (Cr
osslinker 1, 2) with the composition shown in Tables 5 to 7
C-430 (manufactured by Sumitomo 3M) was dissolved in a solvent containing 0.05% by weight to prepare a resist material.
By filtering with a 2 μm Teflon filter,
Each resist solution was prepared.

The resist solution thus obtained was spin-coated on a silicon wafer and applied to a thickness of 0.3 μm. Then, the silicon wafer was baked at 100 ° C. for 90 seconds using a hot plate. ArF excimer laser stepper (Nikon, NA = 0.5)
5) was exposed to light, baked at 110 ° C. for 90 seconds (PEB), and developed with an aqueous solution of 2.38% tetramethylammonium hydroxide, whereby a pattern could be obtained. The obtained resist pattern was evaluated as follows. The results are shown in Tables 5-7. Evaluation method: First, the sensitivity was obtained. Next, the exposure amount for resolving a 0.20 μm line and space at a ratio of 1: 1 was taken as the optimum exposure amount (Eop), and the minimum line width of the separated line and space in this exposure amount was taken as the resolution of the evaluation resist. . The shape of the resolved resist pattern was observed using a scanning electron microscope. In addition, the roughness of 0.20 μm line and space (edge roughness) was measured by a scanning electron microscope with a length measuring function (Hitachi, S7280).

From the results of Tables 5 to 7, it was confirmed that the resist material of the present invention has a pattern having high resolution and no unevenness (small edge roughness).

[0298]

[Chemical 108]

[0299]

[Chemical 109]

[0300]

[Chemical 110]

[0301]

[Chemical 111]

[0302]

[Table 5]

[0303]

[Table 6]

[0304]

[Table 7] PGMEA: Propylene glycol methyl ether acetate EL: Ethyl lactate EIPA: 1-Ethoxy-2-propanol

[ Reference Example 60 ] OFPR was used as a lower layer resist material on a silicon wafer.
Apply 800 (manufactured by Tokyo Ohka) to a thickness of 1.0 μm,
It was heated at 300 ° C. for 5 minutes to be cured. The resist material used in Reference Example 30 was applied onto the lower resist film in a thickness of 0.3 μm by the same method as described above, and prebaked.
Then, 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 no trailing was observed.

After that, 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 /
The resist film has a thickness of 15 nm / mi
It was n or less. By etching for 15 minutes, the lower resist film which was not covered with the present resist film completely disappeared, and a two-layer resist pattern having a thickness of 1 μm or more could be formed. The etching conditions are shown below. Gas flow rate: 50 sccm, gas pressure: 1.3 Pa, rf
Power: 50W, dc bias: 450V

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Toshinobu Ishihara 28-1 Nishifukushima, Nishikofukushima, Nakakubiki-gun, Niigata Pref. 28-1 Nishi-Fukushima 28-1 Shin-Etsu Chemical Co., Ltd. Synthetic Technology Research Institute (72) Inventor Jun Hatakeyama 28-1 Nishi-Fukushima, Nakatsuki-gun, Niigata Prefecture Shin-Etsu Chemical Co., Ltd. Synthetic Technology Research Institute (72) Inventor Nagura Shigehiro 28-1 Nishi-Fukushima, Kubiki-mura, Nakakubiki-gun, Niigata Prefecture Shin-Etsu Chemical Co., Ltd. Synthetic Technology Research Laboratory (56) Reference JP-A-10-324748 (JP, A) JP-A-8-160623 (JP, A) JP-A-11-60734 (JP, A) JP-A-4-106549 (JP, A) JP-A-4-107460 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08 G 77/00-77/62 C08L 83/00-83/16

Claims (15)

(57) [Claims] 1. A repeating unit represented by the following general formula (1), having a weight average molecular weight of 1,000 to 50,000.
A polymeric silicone compound that is 0. [Chemical 1] [In the formula, Z is a divalent to hexavalent non-aromatic monocyclic or polycyclic hydrocarbon group having 5 to 12 carbon atoms or a bridged cyclic hydrocarbon group, and Z ′ is a divalent to hexavalent one. A linear or branched hydrocarbon group having 1 to 20 carbon atoms, or a non-aromatic monocyclic or polycyclic hydrocarbon group having 3 to 20 carbon atoms or a bridged cyclic hydrocarbon group, These groups may have a nitrogen atom, an oxygen atom or a sulfur atom interposed between carbon-carbon bonds,
A hydrogen atom on a carbon atom is a halogen atom, an alkoxy group,
It may be substituted with a nitro group, a cyano group or an acetyl group, and the methylene group in the carbon skeleton may be substituted with a carbonyl group. x, y, and z each represent an integer of 1 to 5, depending on the valence of Z and Z ′. R ¹ is a group represented by the following general formula (2a) or (2b), R ² is a group having 1 to 1 carbon atoms.
8 straight-chain, branched or cyclic, unsubstituted or substituted alkyl or alkenyl groups, or C 5-12 non-aromatic monovalent polycyclic hydrocarbon groups or bridged cyclic hydrocarbons Indicates a group. [Chemical 2] (In the formula, R represents a hydrogen atom, a hydroxyl group or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and R'is a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms. In these alkyl groups and alkylene groups, an oxygen atom may be present in the carbon-carbon bond, or a part of the carbon-bonded hydrogen atoms may be substituted with a hydroxyl group. 'May form a ring with each other, and in the case of forming a ring, R and R'each have 1 to 8 carbon atoms.
Represents a linear or branched alkylene group. ) Expression (1)
, P1 , p2, p4 are positive numbers, p3 is 0 or a positive number, and p1 + p2 + p3 + p4 = 1, and 0 <p1 / (p1 + p2 + p3 + p4) ≦ 0.9 0 <p2 / (p1 + p2 + p3 + p4) ≦ 0.8 0 ≦ It is a number satisfying p3 / (p1 + p2 + p3 + p4) ≦ 0.7 0 <p4 / (p1 + p2 + p3 + p4) ≦ 0.9 . ] 2. A polymer silicone compound comprising a repeating unit represented by the general formula (1) according to claim 1, wherein some or all of the hydrogen atoms of the carboxyl group or the carboxyl group and the hydroxyl group are one type or two or more types. A high molecular weight silicone compound having a weight average molecular weight of 1,000 to 50,000 substituted with an acid labile group. 3. The remainder of the polymer silicone compound represented by the above general formula (1), wherein a part of hydrogen atoms of a carboxyl group or a carboxyl group and a hydroxyl group is partially substituted by one or more acid labile groups. The hydrogen atom of the carboxyl group and / or the hydroxyl group of the formula (1) is in the following general formula (3a) at a ratio of more than 0 mol% and not more than 50 mol% of the hydrogen atoms of the carboxyl group and the hydroxyl group of the whole polymer silicone compound of the formula (1).
The polymer silicone compound according to claim 2, which is crosslinked intramolecularly and / or intermolecularly by being substituted with a group having a COC group represented by (3b). [Chemical 3] (In the formula, R ³ and R ⁴ represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms. Alternatively, R ³ and R ⁴ may form a ring, When forming a ring, R ³ and R ^{4 each} represent a linear or branched alkylene group having 1 to 8 carbon atoms, and R ⁵ represents a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms. Group, 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, The group of may have a heteroatom interposed,
Further, a part of hydrogen atoms bonded to the carbon atom is a hydroxyl group,
It may be substituted with a carboxyl group, an acyl group or a fluorine atom. B is -CO-O-, -NHCO-O
-Or-NHCONH- is shown. c is 2-8, c'is 1
Is an integer of ~ 7. ) 4. A crosslinkable group having a C—O—C group represented by the general formula (3a) or (3b) has the following general formula (3):
The polymer silicone compound according to claim 3, which is represented by a ″ ′) or (3b ′ ″). [Chemical 4] (In the formula, R ³ and R ⁴ represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms. Alternatively, R ³ and R ⁴ may form a ring, When forming a ring, R ³ and R ^{4 each} represent a linear or branched alkylene group having 1 to 8 carbon atoms, and R ⁵ represents a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms. Group, 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. Alternatively, it represents an arylene group having 6 to 30 carbon atoms, and these groups may have a heteroatom interposed therebetween,
Further, a part of hydrogen atoms bonded to the carbon atom is a hydroxyl group,
It may be substituted with a carboxyl group, an acyl group or a fluorine atom. B is -CO-O-, -NHCO-O
-Or-NHCONH- is shown. c '' is 2-4,
c ″ ′ is an integer of 1 to 3. ) 5. The acid labile group is a group represented by the following general formula (4), a group represented by the following general formula (5), and a carbon number of 4 to 2.
A tertiary alkyl group of 0, a trialkylsilyl group having 1 to 6 carbon atoms in each alkyl group, and an oxoalkyl group having 4 to 20 carbon atoms, or one or more kinds of groups. Alternatively, the polymer silicone compound according to item 4. [Chemical 5] (R ⁶ and R ⁷ represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, and R ⁸ represents 1 carbon atom.
~ 18 a monovalent hydrocarbon group which may have a hetero atom, R ⁶ and R ⁷ , R ⁶ and R ⁸ or R ⁷ and R ⁸ may form a ring, When formed, R ⁶ , R ⁷ and R ⁸ each represent a linear or branched alkylene group having 1 to 18 carbon atoms. R ⁹ is a tertiary alkyl group having 4 to 20 carbon atoms, a trialkylsilyl group having 1 to 6 carbon atoms in each alkyl group,
An oxoalkyl group having 4 to 20 carbon atoms or a group represented by the above general formula (4) is shown. a is an integer of 0-6. ) 6. A resist material comprising the polymer silicone compound according to claim 1. Description: 7. (A) Organic solvent (B) Polymeric silicone compound having a repeating unit represented by the following general formula (1) or a carboxyl group of the polymeric silicone compound or a part of hydrogen atoms of the carboxyl group and hydroxyl group Or a weight average molecular weight of 1,000 to 5 which is wholly substituted by one or more kinds of acid labile groups
10,000 high molecular silicone compounds, [In the formula, Z is a divalent to hexavalent non-aromatic monocyclic or polycyclic hydrocarbon group having 5 to 12 carbon atoms or a bridged cyclic hydrocarbon group, and Z ′ is a divalent to hexavalent one. A linear or branched hydrocarbon group having 1 to 20 carbon atoms, or a non-aromatic monocyclic or polycyclic hydrocarbon group having 3 to 20 carbon atoms or a bridged cyclic hydrocarbon group, These groups may have a nitrogen atom, an oxygen atom or a sulfur atom interposed between carbon-carbon bonds,
A hydrogen atom on a carbon atom is a halogen atom, an alkoxy group,
It may be substituted with a nitro group, a cyano group or an acetyl group, and the methylene group in the carbon skeleton may be substituted with a carbonyl group. x, y, and z each represent an integer of 1 to 5, depending on the valence of Z and Z ′. R ¹ is a group represented by the following general formula (2a) or (2b), R ² is a group having 1 to 1 carbon atoms.
8 straight-chain, branched or cyclic, unsubstituted or substituted alkyl or alkenyl groups, or C 5-12 non-aromatic monovalent polycyclic hydrocarbon groups or bridged cyclic hydrocarbons Indicates a group. [Chemical 7] (In the formula, R represents a hydrogen atom, a hydroxyl group or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and R'is a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms. In these alkyl groups and alkylene groups, an oxygen atom may be present in the carbon-carbon bond, or a part of the carbon-bonded hydrogen atoms may be substituted with a hydroxyl group. 'May form a ring with each other, and in the case of forming a ring, R and R'each have 1 to 8 carbon atoms.
Represents a linear or branched alkylene group. ) Expression (1)
, P1 , p2, p4 are positive numbers, p3 is 0 or a positive number, and p1 + p2 + p3 + p4 = 1, and 0 <p1 / (p1 + p2 + p3 + p4) ≦ 0.9 0 <p2 / (p1 + p2 + p3 + p4) ≦ 0.8 0 ≦ It is a number satisfying p3 / (p1 + p2 + p3 + p4) ≦ 0.7 0 <p4 / (p1 + p2 + p3 + p4) ≦ 0.9 . Further, the above general formula (1) in which a part of hydrogen atoms of a carboxyl group or a carboxyl group and a hydroxyl group is partially substituted with one or more kinds of acid labile groups.
In the proportion of more than 0 mol% and not more than 50 mol% of the total hydrogen atoms of the remaining carboxyl groups and / or hydroxyl groups of the polymer silicone compound represented by the following general formula (3a) or (3
It may be crosslinked intramolecularly and / or intermolecularly by substituting with a group having a C—O—C group shown in b). [Chemical 8] (In the formula, R ³ and R ⁴ represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms. Alternatively, R ³ and R ⁴ may form a ring, When forming a ring, R ³ and R ^{4 each} represent a linear or branched alkylene group having 1 to 8 carbon atoms, and R ⁵ represents a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms. Group, 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, The group of may have a heteroatom interposed,
Further, a part of hydrogen atoms bonded to the carbon atom is a hydroxyl group,
It may be substituted with a carboxyl group, an acyl group or a fluorine atom. B is -CO-O-, -NHCO-O
-Or-NHCONH- is shown. c is 2-8, c'is 1
Is an integer of ~ 7. )] (C) A resist material containing an acid generator. 8. The acid labile group is a group represented by the following general formula (4), a group represented by the following general formula (5), and a carbon number of 4 to 2.
8. A tertiary alkyl group of 0, a trialkylsilyl group having 1 to 6 carbon atoms in each alkyl group, and an oxoalkyl group having 4 to 20 carbon atoms, or one or more kinds of groups. Resist material. [Chemical 112] (R ⁶ and R ⁷ represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, and R ⁸ represents 1 carbon atom.
~ 18 a monovalent hydrocarbon group which may have a hetero atom, R ⁶ and R ⁷ , R ⁶ and R ⁸ or R ⁷ and R ⁸ may form a ring, When formed, R ⁶ , R ⁷ and R ⁸ each represent a linear or branched alkylene group having 1 to 18 carbon atoms. R ⁹ is a tertiary alkyl group having 4 to 20 carbon atoms, a trialkylsilyl group having 1 to 6 carbon atoms in each alkyl group,
An oxoalkyl group having 4 to 20 carbon atoms or a group represented by the above general formula (4) is shown. a is an integer of 0-6. ) 9. The resist material according to claim 7, further comprising (D) a dissolution control agent. 10. The resist material according to claim 7, 8 or 9, further comprising (E) a basic compound. 11. (F): ≡C—COO in the molecule
The resist material according to any one of claims 7 to 10, wherein a compound having a group represented by H is mixed. 12. The resist material according to claim 7, further comprising (G): an acetylene alcohol derivative. 13. (A) Organic solvent (B) Polymeric silicone compound having a repeating unit represented by the following general formula (1) or a carboxyl group of the polymeric silicone compound or a part of hydrogen atoms of the carboxyl group and hydroxyl group Is a weight-average molecular weight of 1,000 to 50,000 substituted by one or more acid labile groups.
Polymeric silicone compound of 0, [In the formula, Z is a divalent to hexavalent non-aromatic monocyclic or polycyclic hydrocarbon group having 5 to 12 carbon atoms or a bridged cyclic hydrocarbon group, and Z ′ is a divalent to hexavalent one. A linear or branched hydrocarbon group having 1 to 20 carbon atoms, or a non-aromatic monocyclic or polycyclic hydrocarbon group having 3 to 20 carbon atoms or a bridged cyclic hydrocarbon group, These groups may have a nitrogen atom, an oxygen atom or a sulfur atom interposed between carbon-carbon bonds,
A hydrogen atom on a carbon atom is a halogen atom, an alkoxy group,
It may be substituted with a nitro group, a cyano group or an acetyl group, and the methylene group in the carbon skeleton may be substituted with a carbonyl group. x, y, and z each represent an integer of 1 to 5, depending on the valence of Z and Z ′. R ¹ is a group represented by the following general formula (2a) or (2b), R ² is a group having 1 to 1 carbon atoms.
8 straight-chain, branched or cyclic, unsubstituted or substituted alkyl or alkenyl groups, or C 5-12 non-aromatic monovalent polycyclic hydrocarbon groups or bridged cyclic hydrocarbons Indicates a group. [Chemical 10] (In the formula, R represents a hydrogen atom, a hydroxyl group or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and R'is a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms. In these alkyl groups and alkylene groups, an oxygen atom may be present in the carbon-carbon bond, or a part of the carbon-bonded hydrogen atoms may be substituted with a hydroxyl group. 'May form a ring with each other, and in the case of forming a ring, R and R'each have 1 to 8 carbon atoms.
Represents a linear or branched alkylene group. ) Expression (1)
, P1 , p2, p4 are positive numbers, p3 is 0 or a positive number, and p1 + p2 + p3 + p4 = 1, and 0 <p1 / (p1 + p2 + p3 + p4) ≦ 0.9 0 <p2 / (p1 + p2 + p3 + p4) ≦ 0.8 0 ≦ It is a number satisfying p3 / (p1 + p2 + p3 + p4) ≦ 0.7 0 <p4 / (p1 + p2 + p3 + p4) ≦ 0.9 . Further, the above general formula (1) in which a part of hydrogen atoms of a carboxyl group or a carboxyl group and a hydroxyl group is partially substituted with one or more kinds of acid labile groups.
In the proportion of more than 0 mol% and not more than 50 mol% of the total hydrogen atoms of the remaining carboxyl groups and / or hydroxyl groups of the polymer silicone compound represented by the following general formula (3a) or (3
It may be crosslinked intramolecularly and / or intermolecularly by substituting with a group having a C—O—C group shown in b). [Chemical 11] (In the formula, R ³ and R ⁴ represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms. Alternatively, R ³ and R ⁴ may form a ring, When forming a ring, R ³ and R ^{4 each} represent a linear or branched alkylene group having 1 to 8 carbon atoms, and R ⁵ represents a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms. Group, 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, The group of may have a heteroatom interposed,
Further, a part of hydrogen atoms bonded to the carbon atom is a hydroxyl group,
It may be substituted with a carboxyl group, an acyl group or a fluorine atom. B is -CO-O-, -NHCO-O
-Or-NHCONH- is shown. c is 2-8, c'is 1
Is an integer of ~ 7. )] A resist material comprising (C) an acid generator and (H) a compound which is crosslinked by the action of an acid. 14. The acid labile group is a group represented by the following general formula (4), a group represented by the following general formula (5), and a carbon number of 4 to
20 tertiary alkyl groups, each alkyl group having 1 to 6 carbon atoms
14. The resist material according to claim 13, which is one or two or more groups selected from the trialkylsilyl group and the oxoalkyl group having 4 to 20 carbon atoms. [Chemical 113] (R ⁶ and R ⁷ represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, and R ⁸ represents 1 carbon atom.
~ 18 a monovalent hydrocarbon group which may have a hetero atom, R ⁶ and R ⁷ , R ⁶ and R ⁸ or R ⁷ and R ⁸ may form a ring, When formed, R ⁶ , R ⁷ and R ⁸ each represent a linear or branched alkylene group having 1 to 18 carbon atoms. R ⁹ is a tertiary alkyl group having 4 to 20 carbon atoms, a trialkylsilyl group having 1 to 6 carbon atoms in each alkyl group,
An oxoalkyl group having 4 to 20 carbon atoms or a group represented by the above general formula (4) is shown. a is an integer of 0-6. ) 15. (i) Any one of claims 6 to 14
The step of applying the resist material according to the item 1) on the substrate, and (ii) the step of performing a heat treatment and then exposing with a high energy beam or an electron beam having a wavelength of 300 nm or less through a photomask, and (iii) if necessary. And a step of developing with a developer after heat treatment.