JP3505990B2 - High molecular silicone compound, chemically amplified positive 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 chemically amplified positive resist material used for microfabrication in the manufacturing process of semiconductor devices and the like, and deep ultraviolet rays and KrF excimer laser light (248 nm). ), ArF excimer laser light (193n
m), a chemically amplified positive resist material suitable when using a high energy ray such as an electron beam or an X-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, all of these chemically amplified positive resist materials have high sensitivity and high resolution, but forming a fine pattern with a high aspect ratio is considered in view of the mechanical strength of the pattern obtained from them. It was difficult.

Further, the above polyhydroxystyrene is used as a base resin, and deep ultraviolet rays, electron beams and X-rays are used.
Many chemically amplified positive 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, a part of the phenolic hydroxyl group of polyhydroxybenzylsilsesquioxane, which is a stable alkali-soluble silicone polymer, has been used as a silicone-based chemically amplified positive resist material for solving these problems.
Using a base resin protected with -Boc group,
A silicone-based chemically amplified positive resist composition in which this and an acid generator are combined has been proposed (JP-A-7-11).
8651, SPIE vol. 1952 (1993) 3
77).

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)]).

An example of a silicone-based chemically amplified positive resist material having no phenyl group as the base resin is that disclosed in JP-A-5-323611. This base polymer enables alkali development. Since all the hydrophilic groups such as carboxyl group and hydroxy group necessary for this purpose are protected, many protecting groups must be decomposed in order to dissolve the exposed portion in the developing solution. 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, which occurs when many protective groups are decomposed,
It did not give a resist material having high sensitivity and suitable for fine processing.

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. And a novel polymer silicone compound useful as a base polymer of a chemically amplified positive resist material capable of forming a pattern having excellent heat resistance, a chemically amplified positive resist material containing the compound as a base polymer, and pattern formation The purpose is to provide a method.

[0011]

Means for Solving the Problems and Modes for Carrying Out the Invention As a result of intensive studies to achieve the above-mentioned object, the present inventors have found that they are composed of a repeating unit represented by the following general formula (1) and have a weight average. Aromatic ring-free high molecular weight silicone compound having a molecular weight of 1,000 to 50,000, a chemically amplified positive resist material in which an acid generator is added thereto, particularly a chemically amplified positive resist composition in which a dissolution control agent is added to the acid generator -Type resist materials and chemically-amplified positive-type resist materials obtained by further mixing these with a basic compound increase the resist dissolution contrast, and in particular, increase the dissolution rate after exposure, and further show ≡C-COOH in the molecule. A chemically amplified positive resist composition containing a compound having a group that improves the PED stability of the resist and the edge roughness on the nitride film substrate. , The acetylene alcohol derivative improves the coating properties and storage stability, and thus the silicone chemically amplified positive resist composition according to the present invention has high transparency, high resolution, exposure margin, and process adaptability. The present invention has been accomplished by finding that it is extremely effective, highly practical, and very effective as a resist material for VLSI, which is advantageous for precise microfabrication.

That is, the present invention provides the following polymer silicone compound, a chemically amplified positive resist composition containing the same, and a pattern forming method.

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

[0014]

[Chemical 12] [In the formula, Z is a divalent to hexavalent monocyclic or polycyclic hydrocarbon group having 5 to 12 carbon atoms or a bridged cyclic hydrocarbon group, R ¹ is a linear group having 1 to 8 carbon atoms, A branched or cyclic unsubstituted or substituted alkyl group or alkenyl group is shown. R ² represents an acid labile group, m is 0 or a positive integer, n is a positive integer,
It is a number that satisfies m + n ≦ 5. x is a positive integer.
p1 and p2 are positive numbers, q is 0 or a positive number, and 0 <p1 /
(P1 + p2 + q) ≦ 0.9, 0 <p2 / (p1 + p2
+ Q) ≦ 0.9, 0 ≦ q / (p1 + p2 + q) ≦ 0.
7, a number satisfying p1 + p2 + q = 1. Further, more than 0 mol% and not more than 90 mol% of the total hydrogen atoms of the carboxyl group are intramolecular and / or molecular by the crosslinking group having a C—O—C group represented by the following general formula (2a) or (2b). It may be cross-linked.

[0015]

[Chemical 13] (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, R ⁵ represents a linear or branched alkylene group having 1 to 10 carbon atoms, 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,
A hetero atom may be interposed between these groups, and a part of hydrogen atoms bonded to the carbon atom may be substituted with a hydroxyl group, a carboxyl group, an acyl group or a fluorine atom. B represents -CO-O-, -NHCO-O- or -NHCONH-. c is an integer of 2 to 8 and c'is an integer of 1 to 7. )]

Claim 2: The polymeric silicone compound according to claim 1, comprising a repeating unit represented by the following general formula (3).

[0017]

[Chemical 14] (In the formula, R ¹ , R ² , m, n, x, p1, p2 and q have the same meanings as described above.)

Claim 3: The bridging group having a C-O-C group represented by the general formula (2a) or (2b) is represented by the following general formula (2a "') or (2b"'). Claim 1
Alternatively, the polymer silicone compound according to item 2.

[0019]

[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, R ⁵ represents a linear or branched alkylene group having 1 to 10 carbon atoms, d is 0 or an integer of 1 to 5. A '.
Represents a c ″ -valent linear, branched, or cyclic alkylene group having 1 to 20 carbon atoms, an alkyltriyl group, an alkyltetrayl group, and an arylene group having 6 to 30 carbon atoms. A hetero atom may be interposed, and a part of hydrogen atoms bonded to the carbon atom may be substituted with a hydroxyl group, a carboxyl group, an acyl group or a fluorine atom. B is -CO-O-, -NHCO-O- or -N
HCONH- is shown. c '' is 2-4, c '''is 1-
It is an integer of 3. )

Claim 4: R ² 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
The polymer silicone compound according to claim 1, 2 or 3, which is one or more groups selected from the trialkylsilyl group and the oxoalkyl group having 4 to 20 carbon atoms.

[0021]

[Chemical 16] (R ⁶ and R ⁷ represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to ⁸ carbon atoms, and R ⁸ represents 1 to 1 carbon atoms.
18 represents a monovalent hydrocarbon group which may have 18 heteroatoms, R ⁶ and R ⁷ , R ⁶ and R ⁸ or R ⁷ and R ⁸ may form a ring, and form a ring. In this case, 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 the above general formula (4).
Represents a group represented by. a is an integer of 0-6. )

Claim 5: A part of hydrogen atoms of a carboxyl group of a silicone resin comprising a repeating unit represented by the following general formula (3a) is partially replaced by an acid labile group, and a part of the remaining carboxyl group is replaced. C-obtained by reaction with alkenyl ether compound and / or halogenated alkyl ether compound
The compound is crosslinked intramolecularly and / or intermolecularly with a crosslinkable group having an O—C group, and the total amount of the acid labile group and the crosslinkable group exceeds 0 mol% on average of the entire carboxyl groups in the formula (1). A polymer silicone compound, characterized in that the proportion is 80 mol% or less.

[0023]

[Chemical 17] (In the formula, R ¹ represents straight-chain having 1 to 8 carbon atoms, an unsubstituted or substituted alkyl or alkenyl group, branched or cyclic.
x is a positive integer. p is a positive number, q is 0 or a positive number, and is a number satisfying 0 ≦ q / (p + q) ≦ 0.6 and p + q = 1. )

Claim 6: Obtained by reacting a part of the carboxyl group represented by R of a silicone resin composed of a repeating unit represented by the following general formula (3b) with an alkenyl ether compound and / or a halogenated alkyl ether compound. The compound is crosslinked intramolecularly and / or intermolecularly with a crosslinking group having a C—O—C group, and the total amount of the acid labile group and the crosslinking group is represented by the formula (3a).
Average of all carboxyl groups in
The polymer silicone compound according to claim 5, which has a proportion of not more than mol%.

[0025]

[Chemical 18] (In the formula, R represents a carboxyl group or COOR ² ,
At least one of R is a carboxyl group. R ¹ represents a linear, branched or cyclic, unsubstituted or substituted alkyl group or alkenyl group having 1 to 8 carbon atoms, and R ² represents an acid labile group. x is a positive integer. m ′ is 0 or a positive integer, n ′ is a positive integer, and is a number that satisfies m ′ + n ′ ≦ 5. p3 is a positive number, p4 is 0 or a positive number, q is 0 or a positive number, and 0 <p3 / (p3 + p4 + q) ≦ 0.8,
0 ≦ q / (p3 + p4 + q) ≦ 0.6, 0.4 ≦ (p3
+ P4) / (p3 + p4 + q) ≦ 1, p3 + p4 + q =
It is a number that satisfies 1. )

Claim 7: The hydrogen atom of the carboxyl group represented by R of the silicone resin composed of the repeating unit represented by the following general formula (3c) is removed, and the terminal oxygen atom thereof is represented by the following general formula (2a) or (2b). Is crosslinked intramolecularly and / or intermolecularly by a bivalent or higher valent crosslinking group having a C—O—C group represented by
The polymeric silicone compound according to claim 6, wherein the total amount of the acid labile group and the crosslinking group is more than 0 mol% and not more than 80 mol% on average of all the carboxyl groups in the formula (3a).

[0027]

[Chemical 19] [(In the formula, R represents a carboxyl group or COOR ^2, and at least one of R is a carboxyl group. R ¹
Represents a linear, branched or cyclic unsubstituted or substituted alkyl group or alkenyl group having 1 to 8 carbon atoms, and R ² represents an acid labile group. p31 is a positive number, p32, p4 and q are 0 or a positive number, and 0 <p31 / (p31 + p32 + p4 +
q) ≦ 0.8, 0 ≦ p4 / (p31 + p32 + p4 +
q) ≦ 0.8, 0 ≦ q / (p31 + p32 + p4 + q)
≦ 0.6, 0.4 ≦ (p31 + p32 + p4) / (p3
1 + p32 + p4 + q) ≦ 1, p31 + p32 + p4 +
It is a number that satisfies q = 1. x is a positive integer. m '
Is 0 or a positive integer, n'is a positive integer, and m '
It is a number that satisfies + n ′ ≦ 5. )

[0028]

[Chemical 20] (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, R ⁵ represents a linear or branched alkylene group having 1 to 10 carbon atoms, 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,
A hetero atom may be interposed between these groups, and a part of hydrogen atoms bonded to the carbon atom may be substituted with a hydroxyl group, a carboxyl group, an acyl group or a fluorine atom. B represents -CO-O-, -NHCO-O- or -NHCONH-. c is an integer of 2 to 8 and c'is an integer of 1 to 7. )]

Claim 8: The bridging group having a C—O—C group represented by the general formula (2a) or (2b) is represented by the following general formula (2a ″ ′) or (2b ″ ′). Claim 7
The described polymeric silicone compound.

[0030]

[Chemical 21] (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, R ⁵ represents a linear or branched alkylene group having 1 to 10 carbon atoms, d is 0 or an integer of 1 to 5. A '.
Represents a c ″ -valent linear, branched, or cyclic alkylene group having 1 to 20 carbon atoms, an alkyltriyl group, an alkyltetrayl group, and an arylene group having 6 to 30 carbon atoms. A hetero atom may be interposed, and a part of hydrogen atoms bonded to the carbon atom may be substituted with a hydroxyl group, a carboxyl group, an acyl group or a fluorine atom. B is -CO-O-, -NHCO-O- or -N
HCONH- is shown. c '' is 2-4, c '''is 1-
It is an integer of 3. )

Claim 9: 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 polymeric silicone compound according to any one of claims 5 to 8, 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. .

[0032]

[Chemical formula 22] (R ⁶ and R ⁷ represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to ⁸ carbon atoms, and R ⁸ represents 1 to 1 carbon atoms.
18 represents a monovalent hydrocarbon group which may have 18 heteroatoms, R ⁶ and R ⁷ , R ⁶ and R ⁸ or R ⁷ and R ⁸ may form a ring, and form a ring. In this case, 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 the above general formula (4).
Represents a group represented by. a is an integer of 0-6. )

Claim 10: (A) an organic solvent (B) as a base resin, comprising the polymer silicone compound (C) acid generator according to any one of claims 1 to 9. Chemically amplified positive resist material.

Item 11: The chemically amplified positive type resist material according to Item 10, further comprising (D) a dissolution control agent.

Item 12: The chemically amplified positive type resist material according to Item 10 or 11, further comprising (E) a basic compound.

Claim 13: Further, (F): ≡C in the molecule
13. The chemically amplified positive resist composition according to claim 10, wherein a compound having a group represented by —COOH is blended.

Claim 14: The invention further comprises (G): an acetylene alcohol derivative.
14. The chemically amplified positive resist material according to any one of items 1 to 13.

Claim 15: (i) a step of applying the chemically amplified positive resist composition according to any one of claims 10 to 14 onto a substrate;
i) Then, after heat treatment, a wavelength of 30 is obtained through a photomask.
A pattern forming method comprising: a step of exposing with a high energy ray or an electron beam of 0 nm or less; and (iii) a step of performing a heat treatment as needed 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 which is 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 trailing edge development, pattern size control and pattern shape control can be arbitrarily performed by composition, and chemical amplification positive type with excellent process adaptability. The present invention has been accomplished by finding that it can be used as a resist material.

The present invention will be described in more detail below. The novel polymeric silicone compound of the present invention is a polymeric silicone compound having a repeating unit represented by the following general formula (1).

[0043]

[Chemical formula 23] (In the formula, Z is a divalent to hexavalent monocyclic or polycyclic hydrocarbon group having 5 to 12 carbon atoms or a bridged cyclic hydrocarbon group, R ¹ is a straight chain having 1 to 8 carbon atoms, Represents a branched or cyclic unsubstituted or substituted alkyl group or alkenyl group, R ² represents an acid labile group, m is 0 or a positive integer, n is a positive integer (an integer of 1 or more), and m + n ≦ 5, x is a positive integer, p1 and p2 are positive numbers, q is 0 or a positive number, and 0 <p1 / (p1 + p2 + q) ≦ 0.9, 0 <p
2 / (p1 + p2 + q) ≦ 0.9, 0 ≦ q / (p1 + p
2 + q) ≦ 0.7 and p1 + p2 + q = 1. )

Here, Z is a divalent to hexavalent carbon number 5 to 12
Specific examples of the monocyclic or polycyclic hydrocarbon group or the bridged cyclic hydrocarbon group include the following hydrocarbon groups, but are not limited thereto. That is, as the hydrocarbon group, cyclopentanediyl group, cyclohexanediyl group, cycloheptanediyl group, cyclopentanetriyl group, cyclohexanetriyl group, cycloheptanetriyl group, cyclohexanetetrayl group, cyclohexanepentyl group, cyclohexane Hexayl, cyclooctanediyl, cyclonanonediyl, cyclodecanediyl, cyclooctanetriyl, cyclonanonetriyl, cyclodecanetriyl, norbornanediyl, isobornanediyl, norbornanetriyl , An isobornanetriyl group, an 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 [5,2,2]
1,0 ^2,6 ] decane methylenetriyl group and the like.

A preferred example is a polymeric silicone compound having a repeating unit represented by the following general formula (3).

[0046]

[Chemical formula 24] (In the formula, R ¹ , R ² , m, n, x, p1, p2 and q have the same meanings as described above.)

Here, the linear, branched or cyclic unsubstituted alkyl group or alkenyl group having 1 to 8 carbon atoms represented by R ¹ is a methyl group, an ethyl group, a propyl group, an isopropyl group or an n-butyl group. , Isobutyl group, tert-butyl group, cyclohexyl group, cyclopentyl group, vinyl group,
Allyl group, propenyl group, butenyl group, hexenyl group,
A cyclohexenyl group etc. can be illustrated. Examples of the substituted alkyl group or alkenyl group include those in which some or all of the hydrogen atoms of these unsubstituted alkyl group or alkenyl group are substituted with, for example, a cyano group, a nitro group, an alkoxy group having 1 to 5 carbon atoms, or the like. be able to. In addition, x is an integer, and is preferably 1 to 3, particularly preferably 1 or 2. In the above formula (1), p1 and p2 are positive numbers, q is 0 or a positive number, and p1 +
It is a number that satisfies p2 + q = 1. That is, p1, p2, q
Represents the ratio of the p1 repeating unit, the p2 repeating unit, and the q repeating unit of the compound of the present invention, and 0 ≦ q / (p1 + p2 + q) ≦ 0.7, particularly 0 ≦ q
/(P1+p2+q)≦0.6, and when it exceeds 0.7, it becomes insoluble in alkali and is not suitable as a base polymer for resist. Also, q / (p1 + p2 +
If q) is too low, the heat resistance may decrease. Also,
0 <p1 / (p1 + p2 + q) ≦ 0.9, more preferably 0.3 <p1 / (p1 + p2 + q) ≦ 0.8, 0 <p
2 / (p1 + p2 + q) ≦ 0.9, more preferably 0.
2 <p2 / (p1 + p2 + q) ≦ 0.7. 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 acid labile group for R ² is selected variously, 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.

[0049]

[Chemical 25]

In the formula, R ⁶ and R ⁷ are hydrogen atoms or have 1 to 1 carbon atoms.
8, preferably 1 to 6, and more preferably 1 to 5, a linear, branched or cyclic alkyl group, wherein 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.

Examples of the linear, branched or cyclic alkyl group having 1 to 8 carbon atoms represented by R ⁶ and R ⁷ include the same groups as those described for R ¹ .

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.

[0053]

[Chemical formula 26]

As the tertiary alkyl group having 4 to 20 carbon atoms for R ⁹ , 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 trimethylsilyl group, triethylsilyl group, dimethyl-tert-butyl group, and the like, and as the oxoalkyl group having 4 to 20 carbon atoms. , 3-
Examples thereof include an oxocyclohexyl group and a group represented by the following formula.

[0056]

[Chemical 27]

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.

In the above general formula (1), more than 0 mol% and not more than 90 mol%, preferably more than 0 mol% and not more than 80 mol%, more preferably 1 to 60 mol of the total hydrogen atoms of the carboxyl group. % Is the general formula (2a) or (2
It may be crosslinked intramolecularly and / or intermolecularly by a crosslinking group having a C—O—C group shown in b).

The polymer compound having the crosslinking group will be described in more detail. As the polymer silicone compound, a part of the hydrogen atoms of the carboxyl group of the silicone resin having the repeating unit represented by the following general formula (3a) is used. Intramolecular and / or by a bridging group partially substituted with an acid labile group and having a C—O—C group obtained by reacting a part of the remaining carboxyl group with an alkenyl ether compound and / or a halogenated alkyl ether compound. Or, it is crosslinked between molecules, and the total amount of the acid labile group and the crosslinkable group is 0 on average for all the carboxyl groups in the formula (1).
A polymer silicone compound having a ratio of more than mol% and not more than 80 mol% can be used.

[0060]

[Chemical 28] (In the formula, R ¹ represents a linear, branched, or cyclic unsubstituted or substituted alkyl group or alkenyl group having 1 to 8 carbon atoms as described above. X is a positive integer. P and q are positive. It is a number and satisfies 0 ≦ q / (p + q) ≦ 0.6 and p + q = 1.)

In the above formula (3a), p and q are positive numbers and are numbers satisfying p + q = 1. That is, p, q
Represents the ratio of the repeating unit of p and the repeating unit of q of the compound of the present invention, and 0 ≦ q / (p + q) ≦
It is preferable that 0.6, particularly 0 ≦ q / (p + q) ≦ 0.5. In this case, if q / (p + q) ≦ 0.6 is exceeded, it becomes insoluble in alkali and is not suitable as a base polymer for resist. Further, if q / (p + q) is too low, the heat resistance may decrease, so it is more effective that q / (p + q) is 0.2 or more. By appropriately selecting the values of p and q within the above range, pattern size control and pattern shape control can be arbitrarily performed.

Specific examples of such a polymeric silicone compound include a part of the carboxyl group represented by R of a silicone resin having a repeating unit represented by the following general formula (3b), an alkenyl ether compound and / or a halogenated compound. C obtained by reaction with an alkyl ether compound
The compound is crosslinked intramolecularly and / or intermolecularly with a crosslinkable group having a —O—C group, and the total amount of the acid labile group and the crosslinkable group is 0 mol% on average of the entire carboxyl groups in the formula (1).
It is possible to obtain a high molecular silicone compound having a ratio of over 80 mol%.

[0063]

[Chemical 29] (In the formula, R represents a carboxyl group or COOR ² ,
At least one of R is a carboxyl group. R ¹ represents a linear, branched or cyclic, unsubstituted or substituted alkyl group or alkenyl group having 1 to 8 carbon atoms, and R ² represents an acid labile group. x is a positive integer. m ′ is 0 or a positive integer, n ′ is a positive integer, and is a number that satisfies m ′ + n ′ ≦ 5. p3 is a positive number, p4 is 0 or a positive number, q is 0 or a positive number, and 0 <p3 / (p3 + p4 + q) ≦ 0.8,
0 ≦ q / (p3 + p4 + q) ≦ 0.6, 0.4 ≦ (p3
+ P4) / (p3 + p4 + q) ≦ 1, p3 + p4 + q =
It is a number that satisfies 1. Note that p3 + p4 = p,
p is as described above. Further, examples of the cross-linking group having a C—O—C group include those represented by the following general formula (2a) or (2b).

[0064]

[Chemical 30] (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, R ⁵ represents a linear or branched alkylene group having 1 to 10 carbon atoms, d is 0 or an integer of 1 to 10. A
Is a c-valent aliphatic or alicyclic saturated hydrocarbon group having 1 to 50 carbon atoms, an aromatic hydrocarbon group or a heterocyclic group (preferably a linear or branched alkylene group having 1 to 20 carbon atoms, An alkyltriyl group, an alkyltetrayl group, or an arylene group having 6 to 30 carbon atoms), these groups may have a heteroatom interposed, and a part of hydrogen atoms bonded to the carbon atom is It may be substituted with a hydroxyl group, a carboxyl group, an acyl group or a fluorine atom.
B is -CO-O-, -NHCO-O- or -NHCON
H-indicates. c is an integer of 2 to 8 and c'is an integer of 1 to 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. A specific example of A will be described later. The crosslinking groups (2a) and (2b) are derived from the alkenyl ether compound and halogenated alkyl ether compound described later.

The bridging group is not limited to divalent, as is apparent from the value of c'in the above formulas (2a) and (2b), but is not limited to trivalent to trivalent.
It may be an octavalent group. For example, as the divalent bridging group, the following formulas (2a ′) and (2b ′) can be given as the trivalent bridging group.
Examples include those represented by the following formulas (2a ″) and (2b ″).

[0067]

[Chemical 31] The preferred crosslinking group is represented by the following general formula (2a ′ ″) or (2b ′ ″).

[0068]

[Chemical 32] (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, R ⁵ represents a linear or branched alkylene group having 1 to 10 carbon atoms, d is 0 or an integer of 1 to 5. A '.
Represents a c ″ -valent linear, branched, or cyclic alkylene group having 1 to 20 carbon atoms, an alkyltriyl group, an alkyltetrayl group, and an arylene group having 6 to 30 carbon atoms. A hetero atom may be interposed, and a part of hydrogen atoms bonded to the carbon atom may be substituted with a hydroxyl group, a carboxyl group, an acyl group or a fluorine atom. B is -CO-O-, -NHCO-O- or -N
HCONH- is shown. c '' is 2-4, c '''is 1-
It is an integer of 3. )

Specific examples of the polymeric silicone compound of the above formula (3a) of the present invention include the following general formula (3
The hydrogen atom of the carboxyl group represented by R of the silicone resin having the repeating unit represented by c) is removed and the terminal oxygen atom thereof has a C—O—C group represented by the following general formula (2a) or (2b). The compound is crosslinked intramolecularly and / or intermolecularly with a divalent or higher valent crosslinking group, and the total amount of the acid labile group and the crosslinking group exceeds 80 mol% of the average of all carboxyl groups in the formula (3a). Polymeric silicone compounds having the following ratios can be mentioned.

[0070]

[Chemical 33] (In the formula, R represents a carboxyl group or COOR ² ,
At least one of R is a carboxyl group. R ¹ represents a linear, branched or cyclic, unsubstituted or substituted alkyl group or alkenyl group having 1 to 8 carbon atoms, and R ² represents an acid labile group as described above. p31 is a positive number, p32, p4,
q is 0 or a positive number, and 0 <p31 / (p31 + p32
+ P4 + q) ≦ 0.8, 0 ≦ p4 / (p31 + p32 +
p4 + q) ≦ 0.8, 0 ≦ q / (p31 + p32 + p4
+ Q) ≦ 0.6, 0.4 ≦ (p31 + p32 + p4) /
(P31 + p32 + p4 + q) ≦ 1, p31 + p32 +
It is a number that satisfies p4 + q = 1. x is a positive integer. m ′ is 0 or a positive integer, n ′ is a positive integer, and is a number that satisfies m ′ + n ′ ≦ 5. Note that p31
+ P32 = p3, and p3 is as described above. )

Although p31, p32, p4 and q represent the above-mentioned numbers, more preferably, the values of p31, p32, p4 and q are as follows.

[0072]

[Formula 1]

Examples of this polymer compound include those represented by the following formulas (3'-1) and (3'-2).

[0074]

[Chemical 34]

[0075]

[Chemical 35]

In the above formula, p41 and p42 are each 0 or a positive number, but p41 and p42 are never 0 at the same time. p41 + p42 = p4. Expression (3 '
-1) represents an intermolecular bond, and Formula (3'-2) represents an intramolecular bond, which may be used alone or in combination. Here, p41 / (p41 + p42) is preferably 0.1 to 1, more preferably 0.5 to 1, and still more preferably 0.7 to 1.

Q is a bridging group having a C—O—C group, typically a bridging group represented by the above formula (2a) or (2b), and in particular, a formula (2a ′), (2b ′) or (2a ′). '), (2
b ″), preferably (2a ′ ″), (2b ″ ′)
Is a cross-linking group. In this case, when the bridging group has a valence of 3 or more, in the above formula (3a), Q is bonded to 3 or more of the following units.

[0078]

[Chemical 36]

The polymeric silicone compound of the above formula (3a) of the present invention is one in which some hydrogen atoms of the carboxyl group are substituted with an acid labile group and a crosslinking group having the above C--O--C group. However, more preferably, the total of the acid labile group and the crosslinkable group is more than 0 mol% and not more than 80 mol% on average, particularly 2 to 40 mol% with respect to the entire carboxyl group in the formula (3a). It is preferable.

In this case, the proportion of the crosslinking group having a C--O--C group with respect to the entire carboxyl group in the formula (3a) is more than 0 mol% and not more than 80 mol% on average, and preferably 1 to 20 mol%. When it is 0 mol%, the contrast of the alkali dissolution rate becomes small, the advantages of the crosslinking group cannot be taken out, and the resolution becomes poor. On the other hand, if it exceeds 80 mol%, gelation occurs due to excessive cross-linking, solubility in alkali is lost, film thickness change or film stress or bubbles are generated during alkali development, and there are few hydrophilic groups. Therefore, the adhesion to the substrate may be poor.

The ratio of the acid labile group to the entire carboxyl group in the formula (3a) exceeds 0 mol% on average and 80
It is preferably not more than mol%, particularly preferably 10 to 40 mol%. When it is 0 mol%, the contrast of the alkali dissolution rate becomes small and the resolution becomes poor. On the other hand, if it exceeds 80 mol%, the solubility in alkali may be lost, or the affinity with the developing solution may decrease during alkali development, resulting in poor resolution.

The cross-linking group having a C—O—C group and the acid labile group can be arbitrarily controlled in pattern size and pattern shape by appropriately selecting the values 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.

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 above formula (1) of the present invention will be described. This polymeric silicone compound has a divalent to hexavalent carbon number of 5 to 6 and a carboxylic acid alkyl ester group bonded thereto. By hydrolyzing a trichlorosilane compound having 12 monocyclic or polycyclic hydrocarbon groups or a bridged cyclic hydrocarbon group and optionally a linear, branched or cyclic alkyl group trichlorosilane compound, After further thermally condensing the hydrolysis condensate, the alkyl ester group is hydrolyzed (KOH, N
aOH etc.) 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.

[0086]

[Chemical 37] (In the formula, R ¹ , p1, p2, q, and x have the same meanings as described above, and in this case, x = m + n.)

Here, the introduction of the acid labile group can be carried out 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, a carboxyl group of the polymeric silicone compound (1 ') obtained by the above polymerization method is used. Introduces an acid labile group represented by the general formula (4) into, and after isolation, has a C—O—C group in a molecule and / or between molecules by a reaction with an alkenyl ether compound or a halogenated alkyl ether compound. A method of crosslinking with a crosslinking group, or a reaction with an alkenyl ether compound or a halogenated alkyl ether compound to cause intramolecular and / or intermolecular crosslinking with a group represented by C—O—C, and after isolation, the compound represented by the general formula (4 ) The method of introducing an acid labile group, or the reaction with an alkenyl ether compound or a halogenated alkyl ether compound and the general formula A method of collectively introducing the acid labile group represented by (4) can be mentioned. The reaction with the alkenyl ether compound or the halogenated alkyl ether compound and the introduction of the acid labile group represented by the general formula (4) are performed. A batch method is preferable. 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 '), 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).

[0090]

[Chemical 38]

Here, R ¹ , Z, R ⁴ , R ⁵ , R ⁷ , R ⁸ ,
p1, p2, q and x have the same meanings as above, and
R ^3a and R ^{6a each} represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 7 carbon atoms.

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.

Specific examples are as follows.

[0095]

[Chemical Formula 39]

[0096]

[Chemical 40]

[0097]

[Chemical 41]

[0098]

[Chemical 42]

The compound represented by the general formula (I) can be prepared according to, 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 the formula (I) include ethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,2-propanediol divinyl ether, 1,3-propanediol divinyl ether and 1,3-butanediol divinyl ether. Vinyl ether, 1,4
-Butanediol divinyl ether, tetramethylene glycol divinyl ether, neopentyl glycol divinyl ether, trimethylolpropane trivinyl ether, trimethylolethane trivinyl ether, hexanediol divinyl ether, 1,4-cyclohexanediol divinyl ether, tetraethylene glycol divinyl ether, Pentaerythritol divinyl ether, pentaerythritol trivinyl ether,
Pentaerythritol tetravinyl ether, sorbitol tetravinyl ether, sorbitol pentavinyl ether, ethylene glycol diethylene vinyl ether, triethylene glycol diethylene vinyl ether, ethylene glycol dipropylene vinyl ether,
Triethylene glycol diethylene vinyl ether, trimethylolpropane triethylene vinyl ether, trimethylolpropane diethylene vinyl ether, pentaerythritol diethylene vinyl ether, pentaerythritol triethylene vinyl ether, pentaerythritol tetraethylene vinyl ether and the following formulas (I-1) to (I-31) Examples of the compound include, but are not limited to.

[0101]

[Chemical 43]

[0102]

[Chemical 44]

[0103]

[Chemical formula 45]

[0104]

[Chemical formula 46]

[0105]

[Chemical 47]

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

[0108]

[Chemical 48] (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).

[0110]

[Chemical 49]

[0111]

[Chemical 50]

In the first method, for example, equation (3
When the polymer silicone compound of a) is obtained, the weight average molecular weight is 1,000 to 50,000, and preferably p31 per mol of the carboxyl group of the polymer compound represented by the following general formula (3 ′). Molar formulas (I), (I
I) alkenyl ether compound and p41 +
By reacting 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.

[0113]

[Chemical 51]

Here, R ¹ , x, p31, p41, p4
2, p32 and q have the same meanings as above, p31 + p
41 + p42 + p32 + q = 1.

[0115]

[Chemical 52]

[0116]

[Chemical 53] In the above formula, Q, m ′, n ′ and other symbols are the same as above.

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.

[0121]

[Chemical 54] (In the formula, R ¹ , R ^{3 to} R ⁵ , R ^6a , R ⁷ , R ⁸ , p 1, p
2, q, x, A, B, c and d each have the same meaning as described above, and Z is a halogen atom (Cl, Br or I). )

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

In the second method, for example, when a polymer silicone compound of the formula (3a) is obtained, a high molecular weight silicone having a repeating unit represented by the general formula (3 ′) having a weight average molecular weight of 1,000 to 50,000 is used. 1 mol of the carboxyl group of the molecular compound, p31 + p41 mol of the general formula (V
I) or (VII), and a halogenated alkyl ether compound represented by the formula (4b) are reacted with p41 mol of the compound represented by the formula (3a′-1),
The polymer compound represented by (3a′-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 mol times with respect to 1 mol of the carboxyl group of the polymer compound represented by the general formula (1 ′) which reacts. 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 acid obtained by reacting the polymer compound having the repeating unit represented by the formula (1 ′) or (3 ′) with the compound represented by the formula (4a) or (4b) A compound having an unstable group, for example, the following formula (3d)
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.

[0128]

[Chemical 55]

The polymer compound obtained by the above-mentioned first or second method, for example, the compound represented by the formula (3a'-1) or (3a'-2) is added to the original general formula (3 ' ) Introduce the acid labile group represented by the general formula (5) by reacting p42 mol of a dialkyl dicarbonate compound, alkoxycarbonylalkyl halide or the like with 1 mol of the carboxyl group of the polymer compound represented by A tertiary alkyl halide, a trialkylsilyl halide, an oxoalkyl compound or the like is reacted to give, for example, a compound represented by the general formula (3b′-1) or (3
The polymer compound represented by b'-2) can be obtained.

[0130]

[Chemical 56]

[0131]

[Chemical 57] In the above formula, Q, m ′, n ′ and other symbols are the same as above.

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 based on 1 mol of the carboxyl group of the original 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 (3 It is possible to carry out tertiary alkylation or oxoalkylation by reacting p42 moles of a tertiary alkylating agent or an oxoalkyl compound with 1 mole 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.

As the acid of the catalyst, hydrochloric acid, sulfuric acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, p-toluenesulfonic acid pyridinium salt and the like are preferable, and the amount thereof is the same as in the general formula (1 ′). ) 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.

[0143]

[Chemical 58]

[0144]

[Chemical 59]

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 polymer silicone compound of the present invention is effective as a base polymer of a chemically amplified positive resist material, and the present invention is a chemically amplified positive resist containing the following components using the polymer silicone compound as a base polymer. Provide the material. (A) Organic solvent (B) As a base resin, the above-mentioned polymeric silicone compound (C) Acid generator and, if necessary, (D) Dissolution control agent (E) Basic compound (F) ≡C-COOH in the molecule Group-containing compound (G) acetylene alcohol derivative

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 controlling 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 (parts by weight, the same applies hereinafter) of the base resin of the component (B).
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.

[0149]

[Chemical 60] (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, and specifically, as an 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 non-nucleophilic counter ions of chloride are halide ions such as chloride ion and bromide ion, triflate, 1,1,1-
Fluoroalkyl sulfonates such as trifluoroethane sulfonate and nonafluorobutane sulfonate, tosylate, benzene sulfonate, 4-fluorobenzene sulfonate, aryl sulfonates such as 1,2,3,4,5-pentafluorobenzene sulfonate, mesylate and butane sulfonate Alkyl sulfonates of

[0151]

[Chemical formula 61] (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).

[0153]

[Chemical formula 62] (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, 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.

[0155]

[Chemical formula 63] (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.

[0157]

[Chemical 64] (In the formula, R ^30a and R ^30b are the same as above.)

[0158]

[Chemical 65] (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 chlorine atom It may have been done. )

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 and the like, and examples of the monocyclic aromatic group include a phenyl group, a pyridyl group and a furyl group.

Specifically, for example, diphenyliodonium trifluoromethanesulfonate, (p-tert-butoxyphenyl) phenyliodonium trifluoromethanesulfonate, diphenyliodonium p-toluenesulfonate, p-toluenesulfonic acid (p-tert-
Butoxyphenyl) phenyliodonium, triphenylsulfonium trifluoromethanesulfonate, trifluoromethanesulfonate (p-tert-butoxyphenyl) diphenylsulfonium, bis (p-tert-butoxyphenyl) phenylsulfonium trifluoromethanesulfonate, trifluoromethanesulfonate tris (P-tert-butoxyphenyl) sulfonium,
Triphenylsulfonium p-toluenesulfonate, p
-Toluenesulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, p-toluenesulfonic acid bis (p-tert-butoxyphenyl) phenylsulfonium, p-toluenesulfonic acid tris (p-ter)
t-butoxyphenyl) sulfonium, triphenylsulfonium nonafluorobutanesulfonate, triphenylsulfonium butanesulfonate, trimethylsulfonium trifluoromethanesulfonate, trimethylsulfonium p-toluenesulfonate, cyclohexylmethyl trifluoromethanesulfonate (2-oxocyclohexyl) Sulfonium, cyclohexylmethyl (2-oxocyclohexyl) sulfonium p-toluenesulfonate, dimethylphenylsulfonium trifluoromethanesulfonate, dimethylphenylsulfonium p-toluenesulfonate, dicyclohexylphenylsulfonium trifluoromethanesulfonate, dicyclohexylphenylsulfonium p-toluenesulfonate , Trifluoromethanesulfone Trinaphthylsulfonium, cyclohexylmethyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, (2-norbornyl) methyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, ethylenebis [methyl (2-oxocyclopentyl) sulfonium trifluoromethanesulfone Nato], onium salts such as 1,2′-naphthylcarbonylmethyltetrahydrothiophenium triflate, bis (benzenesulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, bis (xylenesulfonyl) diazomethane, bis (cyclohexylsulfonyl) Diazomethane, bis (cyclopentylsulfonyl) diazomethane, bis (n-butylsulfonyl) diazomethane, bis (isobutyl) Ruhoniru)
Diazomethane, bis (sec-butylsulfonyl) diazomethane, bis (n-propylsulfonyl) diazomethane, bis (isopropylsulfonyl) diazomethane, bis (tert-butylsulfonyl) diazomethane, bis (n-amylsulfonyl) diazomethane, bis (isoamylsulfonyl) Diazomethane, bis (sec-amylsulfonyl) diazomethane, bis (tert-amylsulfonyl) diazomethane, 1-cyclohexylsulfonyl-1- (tert-butylsulfonyl) diazomethane, 1-cyclohexylsulfonyl-1- (tert-
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,
Sulfonic acid ester derivatives of N-hydroxyimide compounds such as N-hydroxy-1,8-naphthalimidomethylsulfonic acid ester and N-hydroxy-1,8-naphthalimidophenylsulfonic acid ester are preferably used. In addition, the said acid generator can be used individually by 1 type or in combination of 2 or more types. 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, relative to 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 ratio of the hydrogen atom of the phenolic hydroxyl group or the carboxyl group with 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.

[0166]

[Chemical formula 66]

[0167]

[Chemical formula 67]

[0168]

[Chemical 68]

[0169]

[Chemical 69] (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 amount of the above-mentioned dissolution control agent to be added is based on 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 dissolution control agent as described above 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 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.

[0176]

[Chemical 70] (In the formula, R ¹ , R ² , Z, n, m, x, p2, and q are the same as above, but p11 is 0 ≦ p1 / (p1 + p2 + q).
0 or a positive number in the range of ≤1. )

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 another dissolution controlling 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 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.

[0181]

[Chemical 71] (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). X 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. )

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) are as follows: 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.

[0183]

[Chemical 72]

[0184]

[Chemical formula 73]

[0185]

[Chemical 74]

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 into 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 the first
Grade, secondary, tertiary aliphatic amines, mixed amines,
Aromatic amines, heterocyclic amines, nitrogen-containing compounds having a carboxy group, nitrogen-containing compounds having a sulfonyl group,
Examples 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, etc. are exemplified, and as tertiary aliphatic amines, trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine. , Tri-n-butylamine, triisobutylamine, tri-sec-butylamine, tripentylamine, tricyclopentylamine, trihexylamine, tricyclohexylamine,
Triheptylamine, trioctylamine, trinonylamine, tridecylamine, tridodecylamine, tricetylamine, N, N, N ', N'-tetramethylmethylenediamine, N, N, N', N'-tetra Examples include methylethylenediamine, N, N, N ′, N′-tetramethyltetraethylenepentamine, and the like.

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

[0194]

[Chemical 75] (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 46} , R ⁴⁴ and R ⁴⁵ and R ⁴⁶ , and R ⁴⁹ and R ⁵⁰ form a ring, the number of carbon atoms in the ring is 1 to 20, and more preferably 1 to
8 and more preferably 1 to 6, and these rings may be branched with an alkyl group having 1 to 6 carbon atoms, particularly 1 to 4 carbon atoms.

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

As the compound having a group represented by ≡C-COOH in the molecule to be blended as the component (F), for example, one or more compounds selected from the following Group I and Group II should be used. However, the present invention is not limited to these. By blending component (F), PE for resist
The D stability can be improved, and the edge roughness on the nitride film substrate can be improved.

[Group I] In the following general formulas (17) to (26),
Part of the hydrogen atoms of the phenolic hydroxyl group of the compound shown
Or all -R⁵¹ -COOH (R⁵¹ Has 1 to 10 carbon atoms
A straight or branched alkylene group)
And a phenolic hydroxyl group (C) in the molecule and ≡C-C
The molar ratio with the group (D) represented by OOH is C / (C +
D) = Compound of 0.1 to 1.0. [Group II] Compounds represented by the following general formulas (27) to (31)
Compound

[0204]

[Chemical 76]

[0205]

[Chemical 77] (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. )

[0206]

[Chemical 78] (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.

[0208]

[Chemical 79]

[0209]

[Chemical 80]

[0210]

[Chemical 81] (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. )

[0211]

[Chemical formula 82]

[0212]

[Chemical 83]

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.

[0217]

[Chemical 84] (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, more 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 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 chemically amplified positive type resist material of the present invention by employing a known lithography technique, for example, spin coating on a substrate such as a silicon wafer. It is applied so that the film thickness is 0.5 to 2.0 μm, and this is prebaked on a hot plate at 60 to 150 ° C. for 1 to 10 minutes, preferably 80 to 120 ° 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, an excimer laser, an X-ray, or an electron beam is exposed at an exposure amount of about 1 to 200 mJ / cm ² , Preferably 10
After irradiating so as to be about 100 mJ / cm ² , it is post-exposure baked (PEB) on a hot plate at 60 to 150 ° C. for 1 to 5 minutes, preferably 80 to 120 ° C. for 1 to 3 minutes. Further, using a developer of an alkali aqueous solution such as 0.1 to 5%, preferably 2 to 3% tetramethylammonium hydroxide (TMAH),
Immersion (d) for 0.1 to 3 minutes, preferably 0.5 to 2 minutes
ip method, paddle method, spray (sp)
The desired pattern is formed on the substrate by developing by a conventional method such as a ray) method. 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, and 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.

[0226]

EFFECT OF THE INVENTION Since the positive resist material using the polymer silicone compound of the present invention as a base resin is sensitive to high energy rays and is excellent in sensitivity and resolution, it is suitable for fine processing by electron beams or deep ultraviolet rays. It is useful. In particular, since the absorption at the exposure wavelength of 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.
Also, because it has excellent resistance to oxygen plasma etching,
The resist film of the present invention was coated on the lower resist film 2
The layer resist is also characterized in that a fine pattern can be formed with a high aspect ratio.

[0227]

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. Table 1 shows the weight average molecular weight and composition ratio of the obtained polymer.

[0231]

[Table 1]

[0232]

[Chemical 85]

[Synthesis Example 9] 50 g of the polymer obtained in Synthesis Example 1 was dissolved in 180 ml of tetrahydrofuran, and after adding a catalytic amount of p-toluenesulfonic acid, 23.0 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. The obtained polymer had a structure represented by the following rational formula (Polym.1), and in the analysis by ¹ H-NMR, 80% of the hydrogen atoms of the carboxyl group of the polymer compound were ethoxyethylated. Was confirmed.

[Synthesis Examples 10 to 19] In Synthesis Example 9,
The polymer of any of Synthesis Examples 1 to 8 was used, and instead of ethyl vinyl ether, Polymer. A silicone polymer represented by the following rational formula (Polym. 2 to 11) was obtained by the same method except that the compound capable of introducing an acid labile group shown in 2 to 11 was used.

[Synthesis Example 20] 20 g of the polymer obtained in Synthesis Example 1 was dissolved in 200 ml of dimethylformamide, potassium carbonate was added as a solid, and 1.0 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. It has a structure shown in 12), and in ¹ H-NMR analysis, it was confirmed that 75% of the hydrogen atoms of the carboxyl group of the polymer compound were ethoxyethylated and the tert-butylcarbonylation rate was 5%. Was done.

[Synthesis Example 21] 20 g of the polymer obtained in Synthesis Example 1 was dissolved in 200 ml of dimethylformamide, potassium carbonate was added as a solid, and 13.0 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. It has a structure shown in 13), and ¹ H-NMR analysis confirmed that 65% of the hydrogen atoms of the carboxyl group of the polymer compound were ethoxyethylated.

[Synthesis Example 22] 50 g of the polymer obtained in Synthesis Example 1 was dissolved in 180 ml of tetrahydrofuran,
After adding trifluoroacetic anhydride, 18.2 g of t-butyl alcohol was added with stirring at 5 ° C or lower. 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 polymer obtained is
It has a structure represented by the following rational formula (Polym.14), and it was confirmed by ¹ H-NMR analysis that 80% of the hydrogen atoms of the carboxyl group of the polymer compound were tert-butylated.

[Synthesis Example 23] The same procedure as in Synthesis Example 22 was carried out except that the polymer of Synthesis Example 5 was used to obtain a silicone polymer represented by the following rational formula (Polym.15).

[0239]

[Chemical 86]

[0240]

[Chemical 87]

[0241]

[Chemical 88]

[0242]

[Chemical 89]

[0243]

[Chemical 90]

[0244]

[Chemical Formula 91]

[Synthesis Example 24] 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 polymer 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. The polymer was crystallized by acidification with hydrochloric acid, filtered and dried to give poly (3-carboxycyclohexylsilsesquioxane) in a yield of 83.
Obtained in 4 g. The weight average molecular weight of the obtained polymer was 3,
It was 000.

[Synthesis Example 25] Poly [(3-carboxyl
Chlohexylsilsesquioxane)-(cyclohexyl
Synthesis of silsesquioxane)] 3-trichlorosilyl-1-cyclohexylcarboxylic acid
Methyl ester 75.0 g (0.272 mol) and shiku
59.2 g of lohexyltrichlorosilane (0.272 m
ol) is dissolved in 150 g of toluene, and the solution is poured into 300 g of water.
The solution was added dropwise with stirring at temperature. After completion of dropping, reaction mixture
The acidic aqueous layer is separated from the product, then the organic layer is washed with 1 L of water.
After the water layer became neutral, it was washed twice more with water. Existence
The solvent of the organic layer was distilled off by an evaporator. That concentrate
Was heated at 200 ° C. for 2 hours to polymerize. Tetra polymer
Hydrofuran 800g dissolved and dissolved 10%
Add dropwise to 1,000 g of sodium hydroxide solution at 40 ° C.
The methyl ester was hydrolyzed by heating for 3 hours. Acid with hydrochloric acid
To crystallize the polymer, filter and dry it
[(3-carboxycyclohexylsilsesquioxa
Yield))-(cyclohexylsilsesquioxane)]
Obtained in 82.0 g. Weight average molecular weight of the obtained polymer
Was 3,500. Also,¹ For H-NMR analysis
And 3-carboxycyclohexylsilsesquioxa
The composition ratio of benzene / cyclohexylsilsesquioxane is 50
It was / 50 (molar ratio).

[Synthesis Examples 26 to 31] Silicone polymers were obtained in the same manner as in Synthesis Example 25 except that the cyclohexyltrichlorosilane compound was changed as shown in Table 1. Table 2 shows the composition ratio and the weight average molecular weight.

[Synthesis Example 32] 50 g of the polymer obtained in Synthesis Example 24 was dissolved in 180 ml of tetrahydrofuran, a catalytic amount of p-toluenesulfonic acid was added, and the mixture was heated at 20 ° C.
With stirring at 13.7 g of ethyl vinyl ether, 4-
2.5 g of butanediol divinyl ether were added.
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 has a structure represented by the following rational formula (Polym.16), and in the analysis by ¹ H-NMR, 53% of the hydrogen atoms of the carboxyl group of the polymer compound were ethoxyethylated to form a carboxyl group. It was confirmed that 5% of the hydrogen atoms of the group were crosslinked.

[Synthesis Examples 33 to 39] In Synthesis Example 32, instead of ethyl vinyl ether and 4-butanediol divinyl ether, Polym. 17 to 23 by the same method except that the compound capable of introducing an acid labile group and a cross-linking group is used.
A silicone polymer represented by 3) was obtained.

[Synthesis Example 40] 20 g of the polymer obtained in Synthesis Example 32 was dissolved in 200 ml of dimethylformamide, potassium carbonate was added as a solid, and 1.0 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. In the analysis by ¹ H-NMR, 53% of the hydrogen atoms of the carboxyl group of the polymer compound are ethoxyethylated, 5% of the hydrogen atoms of the carboxyl group are crosslinked, and tert- It was confirmed that the butyl carbonylation rate was 5%.

[Synthesis Examples 41 to 47] Silicone polymers represented by the following formula (Polym. 25 to 31) were obtained by the same method as in Synthesis Example 32 except that the base polymers were replaced with Synthesis Examples 25 to 31. .

The structure of the obtained polymer was as shown in the following rational formula, and the respective substitution rates were as shown in Table 3. In the formulas below, R represents a group in which the following units are cross-linked intramolecularly or intramolecularly, and (R) represents a state in which the cross-linking group R is bonded.

[0253]

[Chemical Formula 92]

[0254]

[Table 2]

[0255]

[Table 3]

[0256]

[Chemical formula 93]

[0257]

[Chemical 94]

[0258]

[Chemical 95]

[0259]

[Chemical 96]

[Examples 1 to 56] The polymers (Polym. 1 to 31) obtained in the above synthesis examples were used as a base resin, and the acid generator represented by the following formula (PAG. 1 to 7), the following formula A dissolution control agent represented by (DRR.1,4),
A basic compound, a compound represented by the following formula (ACC.1) and having a group represented by ≡C—COOH in the molecule, is dissolved in propylene glycol methyl ether acetate (PGMEA) with the composition shown in the table to prepare a resist material. Then, each composition was filtered through a 0.2 μm Teflon filter to prepare a resist solution.

Examples 1-27 (Polym. 1-15)
The resist solution thus obtained was spin-coated on a silicon wafer and applied to a thickness of 0.3 μm. Next, this silicon wafer is heated to 100 ° C. using a hot plate.
Baked for 90 seconds. This was exposed using an ArF excimer laser stepper (Nikon Co., NA = 0.55), baked at 110 ° C. for 90 seconds, and developed with a 0.12% tetramethylammonium hydroxide aqueous solution to give a positive image. The pattern of the mold could be obtained. The obtained resist pattern was evaluated as follows. The results are shown in Tables 4 and 5. Evaluation method: First, the sensitivity (Eth) was determined. Then 0.2
The exposure amount for resolving 0 μm line and space at 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. Also, 0.
Scanning electron microscope with a measuring function for unevenness (edge roughness) of 18 μm line and space (Hitachi, S7
280).

Examples 28 to 56 (Polym. 16 to 3)
1 use) The obtained resist solution was spin-coated on a silicon wafer and applied to a thickness of 0.4 μm. Next, this silicon wafer is heated to 100 ° C. using a hot plate.
Baked for 90 seconds. This is an excimer laser stepper (Nikon, NSR-2005EX8A, NA =
0.5), exposed at 110 ° C. for 90 seconds, and developed with an aqueous solution of 2.38% tetramethylammonium hydroxide, a positive pattern could be obtained. The obtained resist pattern was evaluated as follows. The results are shown in Tables 6 and 7. Evaluation method: First, the sensitivity (Eth) was determined. Then 0.2
The exposure amount for resolving a 4 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 at 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. Also, 0.
The roughness (edge roughness) of 25 μm line and space was measured with a scanning electron microscope (Hitachi, S7280).

From the results shown in Tables 4 to 7, it was confirmed that the chemically amplified resist material of the present invention has a pattern having high resolution and no unevenness (small edge roughness).

[0264]

[Chemical 97]

[0265]

[Chemical 98]

[0266]

[Table 4]

[0267]

[Table 5]

[0268]

[Table 6]

[0269]

[Table 7]

[Example 57] A lower layer layer was formed on a silicon wafer.
OFPR as a gist material 800 (made by Tokyo Ohka)
Apply to a thickness of 2.0 μm, heat at 200 ℃ for 5 minutes,
Cured. Used in Example 1 on this lower resist film
The resist material is applied in the same manner as above to a thickness of about 0.35 μm.
Applied and prebaked. Then KrF excimer
Laser exposure and development to form a pattern on the lower resist film.
Formed. At this time, a pattern perpendicular to the lower resist film is used.
You can get a turn and see the appearance of tailing
There wasn't.

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: 50 W, dc bias: 450 V

[Example 58] OFPR800 (manufactured by Tokyo Ohka Kogyo Co., Ltd.) as a lower layer resist material was applied to a silicon wafer to a thickness of 2.0 µm and heated at 200 ° C for 5 minutes.
Cured. The resist material used in Example 28 was applied on the lower resist film in the same manner as described above to a thickness of about 0.35 μm 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 /
min, whereas the resist film is 3 nm / min
It was below. By etching for 15 minutes, the lower layer resist film not covered with the present resist film completely disappeared, and a two-layer resist pattern having a thickness of 2 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

Next, to the resist compositions of Examples 1, 6, 19 and 21 above, 0.05% by weight of Surfynol E1004 (manufactured by Nisshin Chemical Industry Co., Ltd.) having the following structural formula as an acetylene alcohol derivative With respect to the resist composition added so that the amount became%, the storage stability with respect to the increase of particles (foreign matter) was observed. The results are shown in Table 7 below. At this time, KL- is used as an in-liquid particle counter.
20A (manufactured by Rion Co., Ltd.) was used, and the particle size of 0.3 μm or more in an accelerated test by storage at 40 ° C. was monitored.

[0275]

[Chemical 99]

[0276]

[Table 8]

─────────────────────────────────────────────────── ─── 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) References JP-A-62-36662 (JP, A) JP-A-4-107460 (JP, A) JP-A-8-160623 (JP, A) JP-A-9-274319 (JP, A) JP-A-10-207066 (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.
High molecular silicone compound. [Chemical 1] [In the formula, Z is a divalent to hexavalent monocyclic or polycyclic hydrocarbon group having 5 to 12 carbon atoms or a bridged cyclic hydrocarbon group, R ¹ is a linear group having 1 to 8 carbon atoms, A branched or cyclic unsubstituted or substituted alkyl group or alkenyl group is shown. R ² represents an acid labile group, m is 0 or a positive integer, n is a positive integer,
It is a number that satisfies m + n ≦ 5. x is a positive integer.
p1 and p2 are positive numbers, q is 0 or a positive number, and 0 <p1 /
(P1 + p2 + q) ≦ 0.9, 0 <p2 / (p1 + p2
+ Q) ≦ 0.9, 0 ≦ q / (p1 + p2 + q) ≦ 0.
7, a number satisfying p1 + p2 + q = 1. Further, more than 0 mol% and not more than 90 mol% of the total hydrogen atoms of the carboxyl group are intramolecular and / or molecular by the crosslinking group having a C—O—C group represented by the following general formula (2a) or (2b). It may be cross-linked. [Chemical 2] (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, R ⁵ represents a linear or branched alkylene group having 1 to 10 carbon atoms, 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,
A hetero atom may be interposed between these groups, and a part of hydrogen atoms bonded to the carbon atom may be substituted with a hydroxyl group, a carboxyl group, an acyl group or a fluorine atom. B represents -CO-O-, -NHCO-O- or -NHCONH-. c is an integer of 2 to 8 and c'is an integer of 1 to 7. )] 2. The polymeric silicone compound according to claim 1, comprising a repeating unit represented by the following general formula (3). [Chemical 3] (In the formula, R ¹ , R ² , m, n, x, p1, p2 and q have the same meanings as described above.) 3. A crosslinkable group having a C—O—C group represented by the general formula (2a) or (2b) has the following general formula (2):
The polymer silicone compound according to claim 1, which is represented by a ″ ′) or (2b ′ ″). [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, R ⁵ represents a linear or branched alkylene group having 1 to 10 carbon atoms, d is 0 or an integer of 1 to 5. A '.
Represents a c ″ -valent linear, branched, or cyclic alkylene group having 1 to 20 carbon atoms, an alkyltriyl group, an alkyltetrayl group, and an arylene group having 6 to 30 carbon atoms. A hetero atom may be interposed, and a part of hydrogen atoms bonded to the carbon atom may be substituted with a hydroxyl group, a carboxyl group, an acyl group or a fluorine atom. B is -CO-O-, -NHCO-O- or -N
HCONH- is shown. c '' is 2-4, c '''is 1-
It is an integer of 3. ) 4. R ² 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, and each alkyl group having 1 carbon atom. 1 to 2 or more groups selected from a trialkylsilyl group having 6 to 6 and an oxoalkyl group having 4 to 20 carbon atoms.
The high molecular silicone compound according to 2 or 3. [Chemical 5] (R ⁶ and R ⁷ represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to ⁸ carbon atoms, and R ⁸ represents 1 to 1 carbon atoms.
18 represents a monovalent hydrocarbon group which may have 18 heteroatoms, R ⁶ and R ⁷ , R ⁶ and R ⁸ or R ⁷ and R ⁸ may form a ring, and form a ring. In this case, 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 the above general formula (4).
Represents a group represented by. a is an integer of 0-6. ) 5. A silicone resin comprising a repeating unit represented by the following general formula (3a) is partially substituted with an acid labile group for a part of hydrogen atoms of a carboxyl group, and the remaining carboxyl group and an alkenyl ether are partially substituted. In the molecule and / or intermolecularly cross-linked by a cross-linking group having a C-O-C group obtained by the reaction with a compound and / or a halogenated alkyl ether compound, the total of the acid labile group and the cross-linking group. A polymeric silicone compound, characterized in that the amount is in a proportion of more than 0 mol% and not more than 80 mol% on average of the entire carboxyl groups in the formula (1). [Chemical 6] (In the formula, R ¹ represents straight-chain having 1 to 8 carbon atoms, an unsubstituted or substituted alkyl or alkenyl group, branched or cyclic.
x is a positive integer. p is a positive number, q is 0 or a positive number, and is a number satisfying 0 ≦ q / (p + q) ≦ 0.6 and p + q = 1. ) 6. A C-obtained by reacting a part of a carboxyl group represented by R of a silicone resin comprising a repeating unit represented by the following general formula (3b) with an alkenyl ether compound and / or a halogenated alkyl ether compound. The compound is intramolecularly and / or intermolecularly crosslinked by a crosslinking group having an O—C group, and the total amount of the acid labile group and the crosslinking group exceeds 0 mol% on average of the entire carboxyl groups in the formula (3a). The polymer silicone compound according to claim 5, which has a proportion of not more than mol%. [Chemical 7] (In the formula, R represents a carboxyl group or COOR ² ,
At least one of R is a carboxyl group. R ¹ represents a linear, branched or cyclic, unsubstituted or substituted alkyl group or alkenyl group having 1 to 8 carbon atoms, and R ² represents an acid labile group. x is a positive integer. m ′ is 0 or a positive integer, n ′ is a positive integer, and is a number that satisfies m ′ + n ′ ≦ 5. p3 is a positive number, p4 is 0 or a positive number, q is 0 or a positive number, and 0 <p3 / (p3 + p4 + q) ≦ 0.8,
0 ≦ q / (p3 + p4 + q) ≦ 0.6, 0.4 ≦ (p3
+ P4) / (p3 + p4 + q) ≦ 1, p3 + p4 + q =
It is a number that satisfies 1. ) 7. A hydrogen atom of a carboxyl group represented by R of a silicone resin composed of a repeating unit represented by the following general formula (3c) is removed and its terminal oxygen atom is represented by the following general formula (2a) or (2b). Are crosslinked intramolecularly and / or intermolecularly with a divalent or higher valent crosslinking group having a C—O—C group, and the total amount of the acid labile group and the crosslinking group is represented by the formula (3
The polymeric silicone compound according to claim 6, which has a proportion of more than 0 mol% and not more than 80 mol% on average of all the carboxyl groups in a). [Chemical 8] [(In the formula, R represents a carboxyl group or COOR ^2, and at least one of R is a carboxyl group. R ¹
Represents a linear, branched or cyclic unsubstituted or substituted alkyl group or alkenyl group having 1 to 8 carbon atoms, and R ² represents an acid labile group. p31 is a positive number, p32, p4 and q are 0 or a positive number, and 0 <p31 / (p31 + p32 + p4 +
q) ≦ 0.8, 0 ≦ p4 / (p31 + p32 + p4 +
q) ≦ 0.8, 0 ≦ q / (p31 + p32 + p4 + q)
≦ 0.6, 0.4 ≦ (p31 + p32 + p4) / (p3
1 + p32 + p4 + q) ≦ 1, p31 + p32 + p4 +
It is a number that satisfies q = 1. x is a positive integer. m '
Is 0 or a positive integer, n'is a positive integer, and m '
It is a number that satisfies + n ′ ≦ 5. ) [Chemical 9] (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, R ⁵ represents a linear or branched alkylene group having 1 to 10 carbon atoms, 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,
A hetero atom may be interposed between these groups, and a part of hydrogen atoms bonded to the carbon atom may be substituted with a hydroxyl group, a carboxyl group, an acyl group or a fluorine atom. B represents -CO-O-, -NHCO-O- or -NHCONH-. c is an integer of 2 to 8 and c'is an integer of 1 to 7. )] 8. A crosslinkable group having a C—O—C group represented by the general formula (2a) or (2b) has the following general formula (2):
The polymer silicone compound according to claim 7, which is represented by a ″ ′) or (2b ′ ″). [Chemical 10] (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, R ⁵ represents a linear or branched alkylene group having 1 to 10 carbon atoms, d is 0 or an integer of 1 to 5. A '.
Represents a c ″ -valent linear, branched, or cyclic alkylene group having 1 to 20 carbon atoms, an alkyltriyl group, an alkyltetrayl group, and an arylene group having 6 to 30 carbon atoms. A hetero atom may be interposed, and a part of hydrogen atoms bonded to the carbon atom may be substituted with a hydroxyl group, a carboxyl group, an acyl group or a fluorine atom. B is -CO-O-, -NHCO-O- or -N
HCONH- is shown. c '' is 2-4, c '''is 1-
It is an integer of 3. ) 9. 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.
9. 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. The polymeric silicone compound according to any one of 1. [Chemical 11] (R ⁶ and R ⁷ represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to ⁸ carbon atoms, and R ⁸ represents 1 to 1 carbon atoms.
18 represents a monovalent hydrocarbon group which may have 18 heteroatoms, R ⁶ and R ⁷ , R ⁶ and R ⁸ or R ⁷ and R ⁸ may form a ring, and form a ring. In this case, 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 the above general formula (4).
Represents a group represented by. a is an integer of 0-6. ) 10. A chemical amplification comprising (A) an organic solvent (B) as a base resin, and the polymeric silicone compound (C) as an acid generator according to any one of claims 1 to 9. Positive resist material. 11. The chemically amplified positive resist material according to claim 10, further comprising (D) a dissolution control agent. 12. The chemically amplified positive resist composition according to claim 10, further comprising (E) a basic compound. 13. (F): ≡C—COO in the molecule
13. The chemically amplified positive type resist material according to claim 10, wherein a compound having a group represented by H is mixed. 14. The composition according to claim 10, further comprising (G): an acetylene alcohol derivative.
The chemically amplified positive resist material as described in any one of 1. 15. (i) a step of applying the chemically amplified positive resist composition according to claim 10 on a substrate, and (ii) a heat treatment followed by a wavelength of 300 nm through a photomask. A pattern forming method comprising: a step of exposing with a high energy beam or an electron beam below; and (iii) a step of performing a heat treatment as needed and then developing with a developing solution.