JP3463681B2 - 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 compound having one or more acid labile groups, and
Alternatively, by incorporating a polymer compound crosslinked by a crosslinking group having a C—O—C group between the molecules into a resist material as a base resin, the alkali dissolution contrast before and after exposure is significantly high, and the sensitivity and resolution are high. The present invention relates to a chemically amplified positive resist material which has an image property and is particularly excellent in reproducibility as a fine pattern forming material for VLSI production.

[0002]

2. Description of the Related Art In recent years,
Along with higher integration and higher speed of LSIs, finer pattern rules are required, and far-ultraviolet lithography is expected as a next-generation fine processing technology. Far-ultraviolet lithography can also be processed to a size of 0.5 μm or less, and when a resist material having low light absorption is used, it is possible to form a pattern having side walls that are nearly vertical to the substrate.

A recently developed chemically amplified positive resist material using an acid catalyst (Japanese Patent Publication No. 27660/1990).
3-27829, etc.) uses a high-intensity KrF excimer laser as a light source for far-ultraviolet rays, and is particularly promising for far-ultraviolet lithography having excellent sensitivity, resolution, and dry etching resistance. It is expected as a resist material.

As such a chemically amplified positive resist material, a two-component system comprising a base resin and an acid generator, and a three-component system comprising a base resin, an acid generator and a dissolution control agent having an acid labile group are known. Has been.

For example, Japanese Patent Application Laid-Open No. 62-115440 proposes a resist material comprising poly-4-tert-butoxystyrene and an acid generator. As a similar one to this proposal, Japanese Patent Application Laid-Open No. 3-223858 is proposed. Is a two-component resist material comprising a resin having a tert-butoxy group in the molecule and an acid generator, and further JP-A-4-21125.
No. 8 proposes a two-component resist material comprising a methyl group, an isopropyl group, a tert-butyl group, a tetrahydropyranyl group, a trimethylsilyl group-containing polyhydroxystyrene and an acid generator.

Further, in Japanese Patent Laid-Open No. 6-100488, poly [3,4-bis (2-tetrahydropyranyloxy) styrene], poly [3,4-bis (tert-butoxycarbonyloxy) styrene], Poly [3,5-
A resist material comprising a polydihydroxystyrene derivative such as bis (2-tetrahydropyranyloxy) styrene] and an acid generator has been proposed.

However, the base resins of these resist materials have an acid labile group in the side chain, and the acid labile group is decomposed by a strong acid such as tert-butyl group and tert-butoxycarbonyl group. Then, as a result of deactivating by reacting with a basic compound in the air, the acid labile group is less likely to decompose, and the pattern shape of the resist material is likely to be a T-top shape. On the other hand, since alkoxyalkyl groups such as ethoxyethyl groups are decomposed by a weak acid, the effect of basic compounds in the air is small, but the pattern shape remarkably narrows with the passage of time from exposure to heat treatment. And has a bulky group in the side chain, the heat resistance is lowered, and the sensitivity and resolution are not satisfactory, all of which have problems and have not yet been put to practical use. However, there is a need for improvement of these problems.

Although the polymer compound described in JP-A-8-305025 is intended to improve the above problems, the ratio of the substituents of the acid labile group and the crosslinkable group is designed in view of the characteristics of the production method. Difficult, and JP-A-8-253534
The polymer compound described in the publication has a drawback that it causes a by- product of a crosslinking group. That is, in designing a resist composition, a polymer compound having various alkali dissolution rates is required by selecting an acid generator and an additive and setting an addition amount, and further, reproducibility of production of the polymer compound is required. However, the production method described in the above publication has a drawback in that the selection of the acid labile group and the bridging group and the substituent ratio must be restricted.

The present invention has been made in view of the above circumstances.
We provide a chemically amplified positive resist material that has higher sensitivity and resolution than conventional resist materials, exposure margin, process adaptability, and reproducibility, excellent plasma etching resistance, and excellent heat resistance of resist patterns. The purpose is to do.

[0010]

Means for Solving the Problems and Modes for Carrying Out the Invention As a result of extensive studies conducted by the present inventor in order to achieve the above object, the weight average molecular weight obtained by the method described below is 1,000 to 500,000. 1 crosslinked by a crosslinking group having a C—O—C group in a molecule and / or between molecules
A novel polymer compound having one or more kinds of acid labile groups is used as a base resin, and an acid generator, a basic compound, or an intramolecular compound is added to the polymer.

[Chemical 79] A group represented by (hereinafter, simply represented by ≡C-COOH
The chemical amplification positive type resist material containing an aromatic compound having the formula (1 ) enhances the dissolution contrast of the resist film, especially increases the dissolution rate after exposure, and further improves the PED stability of the resist, By improving the edge roughness on the film substrate, and by compounding the acetylene alcohol derivative, the coating property and storage stability are improved, and high resolution, exposure margin, excellent process adaptability, and high practicality are provided. It was found that it is advantageous for precise microfabrication and is very effective as a resist material for VLSI.

That is, the present invention provides the following chemically amplified positive resist material and pattern forming method. Claim 1: (A): Organic solvent (B): A polymer compound having one or more acid labile groups as a base resin further has a C—O—C group in the molecule and / or between the molecules. A polymer compound (C) having a weight average molecular weight of 1,000 to 500,000 which is crosslinked by the crosslinking group having: an acid generator, and the base resin has the following general formula (3).
The hydrogen atom of the phenolic hydroxyl group represented by R of the polymer compound having the repeating unit represented by the formula (4a) or C- whose oxygen atom is represented by the following general formula (4a) or (4b)
It is cross-linked intramolecularly and / or intermolecularly by a cross-linking group having an O—C group, and the total amount of the acid labile group and cross-linking group is less than the total hydrogen atoms of the phenolic hydroxyl group of the following general formula (1). The average ratio is more than 0 mol% and 80 mol% or less, the weight average molecular weight is 1,000 to 500,000, and R ⁴ in the following formula (3) and R ⁴ in the following formula (4a) or (4b). A chemically amplified positive resist material, wherein R ⁸ and R ⁹ are different from each other, and R ⁵ and R ⁸ and R ⁹ are the same or different from each other.

[Chemical 6] (In the formula, R is a hydroxyl group or OR³Group, at least 1
The individual is a hydroxyl group. R¹Represents a hydrogen atom or a methyl group
And R²Is a straight-chain, branched or cyclic chain having 1 to 8 carbon atoms.
Indicates a rukyl group. R³Represents an acid labile group. R^Four, R^FiveIs
Hydrogen atom or linear, branched or cyclic having 1 to 8 carbon atoms
Represents an alkyl group, R⁶Is a hetero atom having 1 to 18 carbon atoms
Represents a monovalent hydrocarbon group which may have^FourWhen
R^Five, R^FourAnd R⁶, R ^FiveAnd R⁶And may form a ring,
To form R^Four, R^Five, R⁶Each has 1 carbon
18 linear or branched alkylene groups are shown. R⁷
Represents a tertiary alkyl group having 4 to 12 carbon atoms. Also, x is
0 or a positive integer, y is a positive integer and satisfies x + y ≦ 5
Is a number to add, k is 0 or a positive integer, m is 0 or a positive integer
Is an integer, n is a positive integer, and satisfies k + m + n ≦ 5
It is the number to add. p1 and p2 are positive numbers, q1 is a positive number, q2
Is 0 or a positive number, and 0 <p1 / (p1 + q1 + q2 +
p2) ≦ 0.8, 0 <q1 / (p1 + q1 + q2 + p
2) ≦ 0.8, 0 ≦ q2 / (p1 + q1 + q2 + p2)
≦ 0.8, a number that satisfies p1 + q1 + q2 + p2 = 1
is there. a is 0 or a positive integer of 1-6. x, y,
k, m and n have the same meanings as described above. )

[Chemical 7] (In the formula, R ⁸ and R ⁹ represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms. Alternatively, R ⁸ and R ⁹ may form a ring, When forming a ring, R ⁸ and R ^{9 each} represent a linear or branched alkylene group having 1 to 8 carbon atoms, and R ¹³ 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, a carbonyl group or a fluorine atom. B is -CO-O-, -NHCO-O-
Or it shows -NHCONH-. c is 2-8, c'is 1
It is an integer of 7. )

[Chemical 8] (In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² represents a linear, branched, or cyclic alkyl group having 1 to 8 carbon atoms. Further, x is 0 or a positive integer, and y is Is a positive integer,
It is a number that satisfies x + y ≦ 5. 2. A chemically amplified positive resist composition according to claim 1, wherein R ⁴ is an ethyl group and R ⁸ is a methyl group. Claim 3: The chemically amplified positive resist composition according to claim 2, wherein R ⁵ and R ⁹ are each a hydrogen atom. Claim ^4: -CR 4 R ⁵ -OR ⁶ is a Hidoropiraniru group, chemically amplified positive resist composition according to claim 1, wherein R ⁸ is a methyl group. Claim 5: An onium salt and / or a diazomethane derivative is blended as the component (C).
5. The chemically amplified positive resist material according to any one of items 1 to 4. [6] The chemically amplified positive resist composition as described in any one of [1] to [5], wherein a basic compound is added as the component (D). [7] The chemically amplified positive resist composition of [6], wherein an aliphatic amine is blended as the component (D). [8] The chemically amplified positive resist according to any one of [1] to [7], wherein an aromatic compound having a group represented by ≡C-COOH in the molecule is blended as the component (E). material. Claim 9: Further, as a base resin other than the components (F) and (B), one or two hydrogen atoms of the phenolic hydroxyl group of the polymer compound having a repeating unit represented by the following general formula (1). An average of 0 due to one or more acid labile groups
9. A polymer compound having a weight average molecular weight of 3,000 to 300,000, which is partially substituted in a proportion of not less than mol% and not more than 80 mol%, is blended.
The chemically amplified positive resist material as described in the item.

[Chemical 9] (In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² represents a linear, branched, or cyclic alkyl group having 1 to 8 carbon atoms. Further, x is 0 or a positive integer, and y is Is a positive integer,
It is a number that satisfies x + y ≦ 5. ] Claim 10: As a component (F), the weight average molecular weight which has the repeating unit shown by the following general formula (10) is 3,0.
The chemically amplified positive resist material according to claim 9, wherein a high molecular compound of 100 to 300,000 is blended.

[Chemical 10] (In the formula, R¹, R², R^Four, R^Five, R⁶Has the same meaning as above
Indicates R¹⁴Is -CR^FourR ^FiveOR⁶Acid labile group different from
Where e and f are 0 or a positive number, g is a positive number, and e + f + g
= 1 and 0 ≦ e / (e + f + g) ≦ 0.5, 0.4
≦ g / (e + f + g) ≦ 0.9. ) Claim 11: Further, (G): a dissolution control agent is blended.
11. The method according to any one of claims 1 to 10, characterized in that
Amplification positive resist material. Claim 12: Further, (H): an ultraviolet absorber is added.
12. The method according to any one of claims 1 to 11, characterized in that
Chemically amplified positive resist material. Claim 13: Further, (I): acetylene alcohol derivative
Any one of claims 1 to 12, wherein the body is blended
The chemically amplified positive resist material as described in 1 above. Claim 14: (I) The chemical increase according to any one of claims 1 to 13.
Applying a width positive resist material onto the substrate, and (i
i) Then, after heat treatment, a wavelength of 30 is obtained through a photomask.
Exposure with high-energy rays or electron rays of 0 nm or less
Process, and (iii) heat treatment if necessary, and then development
And a step of developing with a liquid.
Forming method.

Here, when the above-described polymer compound is blended into the resist material as the base resin, the polymer compound is crosslinked by the crosslinking group having a C--O--C group, so that dissolution inhibition is caused. It has the advantages of high properties and a high dissolution contrast after exposure.

That is, in the case of a polymer in which an alkoxyalkyl group is independently added to the side chain, it is difficult to form a T-top shape because the elimination reaction proceeds with a weak acid, but as described above, it is sensitive to acid. Therefore, there is a drawback that the pattern shape becomes remarkably thin with the lapse of time from exposure to heat treatment. Further, since the effect of inhibiting dissolution with respect to alkali is low, it is necessary to use a high substitution rate material in order to obtain dissolution contrast, which has a drawback of lacking heat resistance. On the other hand, the side chain of the phenolic hydroxyl group is t
In the case of a polymer protected with an ert-butoxycarbonyl group, when it is blended in a resist material, it has the advantages that the alkali dissolution inhibiting property is improved, a dissolution contrast is obtained at a low substitution rate, and the heat resistance is good. However, it is necessary to use an acid generator that generates a strong acid such as trifluoromethanesulfonic acid in order to eliminate it and make it alkali-soluble. When such an acid is used, the T-top shape is likely to occur as described above. It will have the drawback.

For such a polymer, as described above, C in the molecule and / or between molecules obtained by reacting a part of the phenolic hydroxyl group with an alkenyl ether compound or a halogenated alkyl ether compound.
A resist material using a polymer compound cross-linked with a cross-linking group having a —O—C group has a drawback that a polymer having a side chain protected by an acetal group has low heat resistance.
T- in a polymer protected with butoxycarbonyl group
This eliminates the drawback that the top shape is easily formed.

On the other hand, as an effect of the polymer compound used in the chemically amplified positive resist composition of the present invention, the polymer compound of the present invention is crosslinked by a crosslinkable group having an acid labile C--O--C group. , The weight average molecular weight in the unexposed portion of the resist film and the solubility in an alkali developer do not change because it is protected by an acid labile group, but the weight average molecular weight in the exposed portion of the resist film is generated. After being decomposed by an acid, the weight average molecular weight of the alkali-soluble base resin before cross-linking and protection by the acid-labile group is returned with the elimination of the acid-labile group. Since it greatly increases, the dissolution contrast can be increased, and as a result, higher resolution can be achieved.

When the crosslinkable group having a C--O--C group is decomposed by an acid, an alcohol compound (diol, triol, polyol compound, etc.) is produced, and the hydrophilic group causes formation of an alcohol developer. Affinity is improved, and as a result, higher resolution can be achieved.

Further, in designing the resist composition, by selecting the acid generator and the additive and setting the addition amount,
Polymer compounds with various alkaline dissolution rates are required, and reproducibility of the production of the polymer compounds is required. However, by using the above-mentioned polymer compounds, there are restrictions on the selection of acid labile groups and crosslinking groups and substitution. It is possible to design without being restricted by the base ratio.

That is, the chemically amplified positive resist material using the above-mentioned polymer as a base resin is much less likely to have a T-top shape, has a narrow pattern shape, and lacks heat resistance than the conventional ones. It is possible to increase the dissolution contrast of the resist film, and as a result, it has high sensitivity and high resolution, and it is possible to arbitrarily control the pattern dimension and the pattern shape depending on the composition. It is a chemically amplified positive resist material having excellent adaptability and reproducibility.

The present invention will be described in more detail below. The polymer compound used in the novel chemically amplified positive resist composition of the present invention is a polymer compound having one or more acid labile groups, and Intramolecular and / or intermolecular C-
It is a polymer compound having a weight average molecular weight of 1,000 to 500,000, which is crosslinked by a crosslinking group having an O—C group.

The above-mentioned polymer compound is a polymer compound having a repeating unit represented by the following general formula (1), in which some hydrogen atoms of the phenolic hydroxyl group are partially replaced by acid labile groups, and the remaining phenolic compound is A polymer compound obtained by the reaction of a part of the hydroxyl groups with an alkenyl ether compound or a halogenated alkyl ether compound is crosslinked with a crosslinking group having a C—O—C group in the molecule and / or between the molecules. it can.

[0021]

[Chemical 11]

Here, R ¹ represents a hydrogen atom or a methyl group, and R ² represents a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, preferably 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms. Represents a linear, branched or cyclic alkyl group,
Methyl group, ethyl group, propyl group, isopropyl group, n
-Butyl group, iso-butyl group, tert-butyl group,
Examples thereof include cyclohexyl group and cyclopentyl group.
Further, x is 0 or a positive integer, y is a positive integer, and x +
Although y ≦ 5 is satisfied, y is 1 to 3, particularly 1 to
It is preferably 2.

The polymer compound according to the present invention is specifically a polymer compound having a repeating unit represented by the following general formula (2) and a part of the phenolic hydroxyl group represented by R and an alkenyl ether compound or a halogenated compound. It is possible to use a polymer compound obtained by the reaction with an alkyl ether compound, which is cross-linked by a cross-linking group having a C—O—C group in the molecule and / or between the molecules.

[0024]

[Chemical 12] (In the formula, R represents a hydroxyl group or an OR ³ group, and at least 1
The individual is a hydroxyl group. R ¹ represents a hydrogen atom or a methyl group, R ² represents a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, and R ³ represents an acid labile group. Further, x is 0 or a positive integer, y is a positive integer, a number satisfying x + y ≦ 5, k is 0 or a positive integer, m is 0 or a positive integer, and n is a positive integer. It is an integer and is a number that satisfies k + m + n ≦ 5. p and q are positive numbers and satisfy p + q = 1. When n is 2 or more, R ³ may be the same or different. )

Here, specific examples of R ¹ and R ² , and the preferable range of y are as described above, and it is preferable that n is 1 to 2 and m is 0 to 1.

The acid labile group which is substituted with the hydrogen atom of the phenolic hydroxyl group or the acid labile group of R ³ is selected variously, and in particular, groups represented by the following formulas (5) and (6): It is preferably a tert-alkyl group, a trialkylsilyl group, a ketoalkyl group or the like.

[0027]

[Chemical 13]

In the formula, R ⁴ and R ⁵ are hydrogen atoms or have 1 to 1 carbon atoms.
8, preferably 1 to 6, more preferably 1 to 5, a linear, branched or cyclic alkyl group, wherein R ⁶ 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 ⁴ and R ⁵ , R ⁴ and R ⁶ , R ⁵ and R ⁶ may form a ring, When forming a ring, R ⁴ , R ⁵ , R
Each ⁶ 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 ⁷ represents a tertiary alkyl group having 4 to 12 carbon atoms, preferably 4 to 8 carbon atoms, and more preferably 4 to 6 carbon atoms. Also, a
Is an integer of 0 to 6.

R^Four, R^FiveStraight-chain or branched having 1 to 8 carbon atoms
Or, as the cyclic alkyl group, R is ²As explained in
Similar groups are mentioned.

R ⁶ 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.

[0031]

[Chemical 14]

R ⁷ is tert-butyl group, 1-methylcyclohexyl group, 2- (2-methyl) group
Examples thereof include an adamantyl group and a tert-amyl group.

Specific examples of the acid labile group represented by the above formula (5) include 1-methoxyethyl group, 1-ethoxyethyl group, 1-n-propoxyethyl group and 1-i.
so-propoxyethyl group, 1-n-butoxyethyl group, 1-iso-butoxyethyl 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 groups such as 1-ethoxy-1-methyl-ethyl group, tetrahydrofuranyl group, cyclic acetal groups such as tetrahydropyranyl group, and the like, preferably ethoxyethyl group, Examples thereof include butoxyethyl group and ethoxypropyl group. On the other hand, as the acid labile group of the above formula (6), for example, tert
-Butoxycarbonyl group, tert-butoxycarbonylmethyl group, tert-amyloxycarbonyl group, te
Examples include rt-amyloxycarbonylmethyl group.
Further, as the tert-alkyl group, tert-
Examples thereof include a butyl group, a tert-amyl group and a 1-methylcyclohexyl group. Examples of the trialkylsilyl group include those having 1 to 6 carbon atoms in each alkyl group such as a trimethylsilyl group, a triethylsilyl group, and a dimethyl-tert-butylsilyl group. Examples of the ketoalkyl group include a 3-oxocyclohexyl group and a group represented by the following formula.

[0034]

[Chemical 15]

Examples of the bridging group having a C--O--C group include groups represented by the following general formula (4a) or (4b).

[0036]

[Chemical 16] (In the formula, R ⁸ and R ⁹ represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms. Alternatively, R ⁸ and R ⁹ may form a ring, When forming a ring, R ⁸ and R ^{9 each} represent a linear or branched alkylene group having 1 to 8 carbon atoms, and R ¹³ 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, a carbonyl group or a fluorine atom. B is -CO-O-, -NHCO-O-
Or it shows -NHCONH-. c is 2-8, c'is 1
It is an integer of 7. )

Here, as the linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, the same ones as described above can be exemplified. A specific example of A will be described later. The crosslinking groups (4a) and (4b) are derived from the alkenyl ether compound and halogenated alkyl ether compound described later.

The cross-linking group is not limited to divalent, as is clear from the value of c'in the above formulas (4a) and (4b), but trivalent to trivalent to
It may be an octavalent group. For example, as the divalent bridging group, the following formulas (4a ′) and (4b ′) can be given as the trivalent bridging group.
Examples include those represented by the following formulas (4a ″) and (4b ″).

[0039]

[Chemical 17]

As a specific example of the polymer compound according to the present invention, the hydrogen atom of the phenolic hydroxyl group represented by R of the polymer compound having a repeating unit represented by the following general formula (3) is removed. The oxygen atom is represented by the above general formula (4
Examples thereof include polymer compounds that are cross-linked intramolecularly and / or intermolecularly with a cross-linking group having a C—O—C group represented by a) or (4b).

[0041]

[Chemical 18] (In the formula, R is a hydroxyl group or OR³Group, at least 1
The individual is a hydroxyl group. R¹Represents a hydrogen atom or a methyl group
And R²Is a straight-chain, branched or cyclic chain having 1 to 8 carbon atoms.
Indicates a rukyl group. R³Represents an acid labile group. R^Four, R^FiveIs
Hydrogen atom or linear, branched or cyclic having 1 to 8 carbon atoms
Represents an alkyl group, R⁶Is a hetero atom having 1 to 18 carbon atoms
Represents a monovalent hydrocarbon group which may have^FourWhen
R^Five, R^FourAnd R⁶, R ^FiveAnd R⁶And may form a ring,
To form R^Four, R^Five, R⁶Each has 1 carbon
18 linear or branched alkylene groups are shown. R⁷
Represents a tertiary alkyl group having 4 to 12 carbon atoms. p1, p2
Is a positive number, q1 is a positive number, q2 is 0 or a positive number, and 0 <p
1 / (p1 + q1 + q2 + p2) ≦ 0.8, 0 <q1 /
(P1 + q1 + q2 + p2) ≦ 0.8, 0 ≦ q2 / (p
1 + q1 + q2 + p2) ≦ 0.8, p1 + q1 + q2 +
It is a number that satisfies p2 = 1. a is 0 or a positive number of 1 to 6
It is an integer. x, y, k, m, n are the same as above
Indicates the meaning of. Note that p1 + p2 = p, q1 + q2 = q
Is. )

Here, R, R ^{1 to} R ⁷ , x, y, k, m,
Specific examples and preferable ranges of n and a are as described above, but R ⁴
And R ⁸ and R ⁹ are different from each other, and R ⁵ and R ⁸ and R ⁹ are the same or different from each other. Further, p1 and p2 are positive numbers, q1 is a positive number, q2 is 0 or a positive number, and 0 <p1
/(P1+q1+q2+p2)≦0.8, 0 <q1 /
(P1 + q1 + q2 + p2) ≦ 0.8, 0 ≦ q2 / (p
1 + q1 + q2 + p2) ≦ 0.8, p1 + q1 + q2 +
It is a number that satisfies p2 = 1.

More preferably, p1, p2, q1 and q2
The value of is as follows.

[0044]

[Equation 1] Further, q1 / (q1 + q2) is preferably 0 to 1, more preferably 0.5 to 1, and even more preferably 0.7 to 1.

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

[0046]

[Chemical 19]

[0047]

[Chemical 20] The formula (3′-1) represents an intermolecular bond and the formula (3′-2) represents an intramolecular bond, and these may be used alone or in combination.

However, Q is a bridging group having a C--O--C group,
Typically, the cross-linking group represented by the above formula (4a) or (4b), particularly the formula (4a ′), (4b ′) or (4a ″), (4
b ″). In this case, the bridging group is 3
If the valence is higher than or equal to the value, in the above formula (3), 3 of the following units
Q is connected to more than one.

[0049]

[Chemical 21]

In the polymer compound of the present invention, part of the hydrogen atoms of the phenolic hydroxyl group is an acid labile group and the above C--O.
Substituted with a bridging group having a -C group,
More preferably, the total of the acid labile group and the crosslinking group is more than 0 mol% and not more than 80 mol% on average, particularly 2 to 50 mol% with respect to all hydrogen atoms of the phenolic hydroxyl group of the compound of formula (1). Preferably there is.

In this case, the proportion of the cross-linking group having a C--O--C group is more than 0 mol% on average and 80 mol% or less, especially 1 to
20 mol% is preferable. 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%, it will be gelled due to excessive cross-linking, lose its solubility in alkali, cause film thickness change, film stress in the film or generation of bubbles during alkali development,
Since there are few hydrophilic groups, the adhesion to the substrate may be poor.

The proportion of acid labile groups is 0 mol% on average.
To 80 mol% or less, particularly preferably 10 to 50 mol%. When it is 0 mol%, the contrast of the alkali dissolution rate becomes small and the resolution becomes poor. On the other hand, 80 mol%
If it exceeds, the solubility in alkali may be lost, or the affinity with a developing solution at the time of alkali development may be low, resulting in poor resolution.

The dimension of the pattern and the shape of the pattern can be arbitrarily controlled by appropriately selecting the values of the crosslinking group having a C--O--C group and the acid labile group within the above range. In the polymer compound of the present invention, the content of the crosslinkable group having a C—O—C group and the acid labile group affects the contrast of the dissolution rate of the resist film,
It relates to the characteristics of the resist material such as pattern size control and pattern shape.

The polymer compound according to the present invention has a weight average molecular weight of 1,0 (measurement method is as described later).
00-500,000, preferably 3,000-30,
Must be 000. Weight average molecular weight is 1,000
If it does not meet the requirements, the resist material will be inferior in heat resistance,
This is because if it exceeds 500,000, the alkali solubility will decrease and the resolution will deteriorate.

Further, in the polymer compound according to the present invention, the molecular weight distribution (Mw / M) of the base resin before being crosslinked
When n) is wide, it is difficult to design the number of crosslinks due to the presence of a low molecular weight or high molecular weight polymer, and it may be difficult to produce a resist material having the same performance. Therefore, as the pattern rule becomes finer, the influence of such molecular weight and molecular weight distribution tends to increase,
In order to obtain a resist material suitable for use in fine pattern dimensions, the molecular weight distribution is 1.0 to 1.5, particularly 1.0 to
A narrow dispersion of 1.3 is preferable. However, it is not limited to these, and it is of course possible to use those having a molecular weight distribution larger than 1.5.

The method for producing the polymer compound according to the present invention includes, for example, a phenolic hydroxyl group of a polymer compound having a repeating unit represented by the general formula (1) and an acid labile group represented by the general formula (5). Is introduced and, after isolation, is reacted with an alkenyl ether compound or a halogenated alkyl ether compound to induce intramolecular and / or intermolecular C-
Method of crosslinking with a crosslinking group having an OC group, or intramolecular and / or intermolecular crosslinking with a group represented by COC by reaction with an alkenyl ether compound or a halogenated alkyl ether compound, and isolation Then, the method of introducing the acid labile group represented by the general formula (5) or 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 (5) are carried out at once. Examples of the method include a method of performing the reaction with an alkenyl ether compound or a halogenated alkyl ether compound and introduction of the acid labile group represented by the general formula (5) at one time. Further, the polymer compound thus obtained may optionally contain an acid labile group represented by the general formula (6), a tert-alkyl group,
It is also possible to introduce a trialkylsilyl group, a ketoalkyl group or the like.

Specifically, as the first method, the equation (1 ')
A method using a polymer compound having a repeating unit represented by the following formula, an alkenyl ether compound represented by the following general formula (I) or (II), and a compound represented by the following general formula (5a), and a second method, A polymer compound having a repeating unit represented by formula (1 ′) and the following general formula (VI)
Alternatively, a method using a halogenated alkyl ether compound represented by (VII) and a compound represented by the following general formula (5b) can be mentioned.

[0058]

[Chemical formula 22]

Where R ¹ , R ² , R ⁹ , x, y and p
1, p2, q1 and q2 have the same meanings as described above, and p1
+ P2 + q1 + q2 = 1. R ⁵ and R ⁶ have the same meanings as described above, and R ^4a and R ^{8a each} represent a hydrogen atom or a linear, branched, or cyclic alkyl group having 1 to 7 carbon atoms.

Further, in the alkenyl ether compound represented by the formula (I) or (II), A has a c-value (c is 2 to
6) and B is —CO—O—, —NH
CO-O- or -NHCONH- is shown, R < ¹³ > shows a C1-C10 linear or branched alkylene group, d
Represents an integer of 0 or 1 to 10, and c represents an integer of 2 to 8.

Specifically, the c-valent organic group represented by A is preferably a hydrocarbon group having 1 to 50 carbon atoms, particularly 1 to 40 carbon atoms, such as O, NH, N (CH ₃ ), S and SO ₂ . Unsubstituted or hydroxyl group which may have a hetero atom, a carboxyl group, a carbonyl group or a fluorine atom-substituted alkylene group, preferably an arylene group having 6 to 50 carbon atoms, particularly 6 to 40 carbon atoms, and these alkylene groups and arylene groups Examples of the group include a bonded group and a c ″ -valent group (c is an integer of 3 to 8) in which a hydrogen atom bonded to a carbon atom of each of the above groups is eliminated. Further, a c-valent heterocyclic group, this heterocyclic group And a group in which the above hydrocarbon group is bonded.

Specific examples include the followings as A.

[0063]

[Chemical formula 23]

[0064]

[Chemical formula 24]

[0065]

[Chemical 25]

[0066]

[Chemical formula 26]

The compound represented by the general formula (I) can be obtained, for example, from 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.

[0069]

[Chemical 27]

[0070]

[Chemical 28]

[0071]

[Chemical 29]

[0072]

[Chemical 30]

[0073]

[Chemical 31]

On the other hand, the compound represented by the above general formula (II) when B is —CO—O— can be produced by reacting a polyvalent carboxylic acid with a halogenated alkyl vinyl ether. Specific examples of the compound represented by the formula (II) when B is —CO—O— include terephthalic acid diethylene vinyl ether, phthalic acid diethylene vinyl ether, isophthalic acid diethylene vinyl ether, phthalic acid dipropylene vinyl ether, and terephthalic acid dipropylene vinyl ether. Examples thereof include, but are not limited to, isophthalic acid dipropylene vinyl ether, maleic acid diethylene vinyl ether, fumaric acid diethylene vinyl ether, and itaconic acid diethylene vinyl ether.

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

[0076]

[Chemical 32] (R ^8a , R ⁹ and R ¹³ have the same meanings as described above.)

B is --NHCO--O-- or --NHCONH
In the case of −, 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,
Polyethylene such as tolylene diisocyanate, dimer of 2,4-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-tolylene diisocyanate, polymethylene polyphenyl isocyanate and hexamethylene diisocyanate. Isocyanate type, adduct of tolylene diisocyanate and trimethylolpropane, adduct of hexamethylene diisocyanate and water, polyisocyanate adduct type of xylene diisocyanate and trimethylolpropane adduct, etc. be able to.
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).

[0078]

[Chemical 33]

[0079]

[Chemical 34]

In the first method, the polymer compound represented by the general formula (1 ′) having a weight average molecular weight of 1,000 to 500,000 and a molecular weight distribution of 1.0 to 1.5 is preferable. The hydrogen atom of the phenolic hydroxyl group is p1 mol of the general formula (I), (I
The alkenyl ether compound represented by I) is reacted with q1 mol of the compound represented by the general formula (5a) to give, for example, a polymer compound represented by the following general formula (3a′-1) or (3a′-2). Obtainable.

[0081]

[Chemical 35]

[0082]

[Chemical 36] (In the formula, m + n = y, and m, n, x, y, p1, p
2, q1, q2, R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ and Q have the same meanings as described above. )

The reaction solvent is preferably an aprotic polar solvent such as dimethylformamide, dimethylacetamide, tetrahydrofuran or ethyl acetate, and may be used alone or in admixture of two or more.

As the acid of the catalyst, hydrochloric acid, sulfuric acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, p-toluenesulfonic acid pyridinium salt, etc. are preferable, and the amount thereof used is the general formula (1) which reacts. It is preferable that the hydrogen atom of the phenolic hydroxyl group of the polymer compound represented by is 0.1 to 10 mol% with respect to 1 mol of all the hydroxyl groups.

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 in a lump 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 (5a) is not particularly limited, but the compound represented by the general formula (5a) 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 (5a) 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.

[0087]

[Chemical 37] (In the formula, R ¹ , R ² , x, y, p1, p2, q1, q2,
R < ⁴ >, R < ⁵ >, R < ⁶ > and R < ⁸ >, R <^9> , R <^13> , A, B, c, d have the same meanings as described above, and Z is a halogen atom (Cl, Br or I). )

The compounds of the formulas (VI) and (VII) and the compound of the formula (5b) are obtained by adding hydrogen chloride and hydrogen bromide to the compounds of the formulas (I) and (II) and the formula (5a). Alternatively, it can be obtained by reacting hydrogen iodide.

In the second method, the weight average molecular weight is 1,0.
The hydrogen atom of the phenolic hydroxyl group of the polymer compound having a repeating unit represented by the general formula (1 ′) having a molecular weight distribution of from 0.00 to 500,000 and preferably from 1.0 to 1.5 is 1 to 1 of all the hydroxyl groups. By reacting p1 mol of the halogenated alkyl ether compound represented by the general formula (VI) or (VII) with q1 mol of the compound represented by the general formula (5b) per mol, for example, the above 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, 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, diisopropylamine, potassium carbonate and the like are preferable, and the amount of the base used is (p1) per 1 mol of the phenolic hydroxyl group of the polymer compound represented by the general formula (1) which reacts.
It is preferably + q1) mol 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 compound represented by the following formula (7) is obtained by reacting the polymer compound having the repeating unit represented by the formula (1 ′) with the compound represented by the formula (5a) or (5b). Was obtained, which was then isolated and then of formula (I),
Crosslinking may be carried out using the compound represented by (II) or (VI) or (VII).

[0095]

[Chemical 38]

The polymer compound obtained by the first or second method, for example, the compound represented by the formula (3a'-1) or (3a'-2) is added to the general formula (1 ') as necessary. ) The general formula (6) is obtained by reacting 1 mol of the phenolic hydroxyl group of the polymer compound represented by) with q2 mol of a dialkyl dicarbonate compound, an alkoxycarbonylalkyl halide, or the like.
By introducing an acid labile group represented by or reacting with a tert-alkyl halide, a trialkylsilyl halide, a ketoalkyl compound or the like, for example, the compound represented by the general formula (3b′-
The polymer compounds represented by 1) and (3b′-2) can be obtained.

[0097]

[Chemical Formula 39]

[0098]

[Chemical 40]

The method of introducing the acid labile group of the above formula (6) 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 used is q2 per 1 mol of the phenolic hydroxyl group of the polymer compound represented by the general formula (1). It is preferably molar.

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.

Further, the polymer compounds represented by the general formulas (3a'-1) and (3a'-2) obtained by the first or second method may be added to the original general formula (1) if necessary. It is possible to tert-alkylate or ketoalkylate by reacting q2 mol of a tert-alkylating agent or ketoalkyl compound with 1 mol of the phenolic hydroxyl group of the polymer compound represented by ').

The above method is preferably carried out in a solvent in the presence of an acid.

The reaction solvent is preferably an aprotic polar solvent such as dimethylformamide, dimethylacetamide, tetrahydrofuran or ethyl acetate, and may be used alone or in admixture of two or more.

The acid used as the catalyst is preferably hydrochloric acid, sulfuric acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, p-toluenesulfonic acid pyridinium salt, etc. It is preferable that it is 0.1 to 10 mol% with respect to 1 mol of the phenolic hydroxyl group of the polymer compound represented by (4).

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.

The tert-alkylating agent is iso-
Butene, 2-methyl-1-butene, 2-methyl-2-butene and the like can be mentioned, and as the ketoalkyl 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 formulas (3c′-1) and (3c′-2) is directly added to the acid compound represented by the general formula (6) without passing through the polymer compound represented by 2). After introducing a labile group, a tert-alkyl group, a trialkylsilyl group, a ketoalkyl group, etc., an acid labile group represented by the general formula (5) can be introduced, if necessary.

[0111]

[Chemical 41]

[0112]

[Chemical 42] (In the formula, R ¹ , R ² , Q, p1, p2, q1, q2, x,
y has the same meaning as above. )

In the polymer compound according to the present invention, R ³
The acid labile group is not limited to one type, and two or more types can be introduced. In this case, q1 mol of the acid labile group is introduced 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 by the same method as described above. Introducing q2 mol of the above compound makes it possible to obtain a polymer compound in which two or more such acid labile groups are introduced or by repeating such an operation as appropriate.

The chemically amplified positive resist material of the present invention is
The above polymer compound is used as a base polymer and contains the following components. (A): Organic solvent, (B): Polymer compound of the above formula (3) as a base resin, (C): Acid generator, (D): Basic compound, and (E): ≡C in the molecule. An aromatic compound having a group represented by —COOH.

In this case, the resist composition of the present invention may contain one or more of the following components (F) to (I) in addition to the above components (A) to (E). (F): One or more acid labile hydrogen atoms of the phenolic hydroxyl group of the polymer compound having the repeating unit represented by the following general formula (1) as a base resin different from the component (B). Weight average molecular weight of 3,000 which is partially substituted with a group as a whole in an average of 0 mol% to 80 mol% inclusive.
0 to 300,000 polymer compounds.

[0116]

[Chemical 43] (In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² represents a linear, branched, or cyclic alkyl group having 1 to 8 carbon atoms. Further, x is 0 or a positive integer, and y is Is a positive integer,
It is a number that satisfies x + y ≦ 5. ) (G): Dissolution control agent. (H): UV absorber. (I): 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 control agent and the like can be dissolved. Examples of such an organic solvent include ketones such as cyclohexanone and methyl-2-n-amyl ketone, 3-methoxybutanol, 3-methyl-3-methoxybutanol, and 1
-Alcohols such as methoxy-2-propanol, 1-ethoxy-2-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, etc. , Propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl-3-methoxypropionate, ethyl-3-ethoxypropionate, acetic acid ter
Examples thereof include esters such as t-butyl, tert-butyl propionate, and propylene glycol monotert-butyl ether acetate, and these can be used alone or in combination of two or more, but are not limited thereto. Not something that is done. In the present invention, among these organic solvents, the solubility of the acid generator in the resist component is the best, diethylene glycol dimethyl ether and 1-
In addition to ethoxy-2-propanol and ethyl lactate, propylene glycol monomethyl ether acetate which is a safety solvent and a mixed solvent thereof are preferably used.

The amount of the organic solvent used is 100% of the base resin (the total amount of the above components (B) and (D), the same applies hereinafter).
200 to 1,000 with respect to parts (weight parts, the same applies hereinafter)
Parts, especially 400 to 800 parts are preferred.

Examples of the acid generator as the component (C) include diphenyliodonium trifluoromethanesulfonate,
Trifluoromethanesulfonic acid (p-tert-butoxyphenyl) phenyliodonium, p-toluenesulfonic acid diphenyliodonium, p-toluenesulfonic acid (p-tert-butoxyphenyl) phenyliodonium, trifluoromethanesulfonic acid triphenylsulfonium, trifluoromethanesulfone Acid (p-te
rt-Butoxyphenyl) diphenylsulfonium, bis (p-tert-butoxyphenyl) phenylsulfonium trifluoromethanesulfonate, tris (p-tert-butoxyphenyl) sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, p- Toluenesulfonic acid (p-ter
t-butoxyphenyl) diphenylsulfonium, p-
Bis (p-tert-butoxyphenyl) phenylsulfonium toluenesulfonate, tris (p-tert-butoxyphenyl) sulfonium p-toluenesulfonate, triphenylsulfonium nonafluorobutanesulfonate, triphenylsulfonium butanesulfonate,
Trimethylsulfonium trifluoromethanesulfonate, trimethylsulfonium p-toluenesulfonate,
Cyclohexylmethyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, cyclohexylmethyl (2-oxocyclohexyl) sulfonium p-toluenesulfonate, dimethylphenylsulfonium trifluoromethanesulfonate, dimethylphenylsulfonium p-toluenesulfonate, trifluoromethanesulfonic acid Onium salts such as dicyclohexylphenylsulfonium and dicyclohexylphenylsulfonium p-toluenesulfonate, 2-cyclohexylcarbonyl-2- (p-toluenesulfonyl) propane, 2
Β-ketosulfone derivatives such as -iso-propylcarbonyl-2- (p-toluenesulfonyl) propane, bis (benzenesulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (n-butyl) Sulfonyl) diazomethane, bis (iso-butylsulfonyl)
Diazomethane derivatives such as diazomethane, bis (sec-butylsulfonyl) diazomethane, bis (n-propylsulfonyl) diazomethane, bis (iso-propylsulfonyl) diazomethane, bis (tert-butylsulfonyl) diazomethane, disulfones such as diphenyldisulfone and dicyclohexyldisulfone. Derivatives, nitrobenzyl sulfonate derivatives such as 2,6-dinitrobenzyl p-toluenesulfonate and 2,4-dinitrobenzyl p-toluenesulfonate, 1,2,3-tris (methanesulfonyloxy) benzene, 1,2,2. 3-tris (trifluoromethanesulfonyloxy) benzene,
1,2,3-tris (p-toluenesulfonyloxy)
Sulfonate derivative such as benzene, phthalimido-yl-triflate, phthalimido-yl-tosylate, 5-norbornene-2,3-dicarboximide-
Examples thereof include imide-yl-sulfonate derivatives such as yl-triflate, 5-norbornene-2,3-dicarboximido-yl-tosylate, and 5-norbornene-2,3-dicarboximido-yl-n-butyl sulfonate. However, triphenylsulfonium trifluoromethanesulfonate, trifluoromethanesulfonic acid (p-
tert-butoxyphenyl) diphenylsulfonium, trifluoromethanesulfonic acid tris (p-ter)
t-butoxyphenyl) sulfonium, p-toluenesulfonate triphenylsulfonium, p-toluenesulfonate (p-tert-butoxyphenyl) diphenylsulfonium, p-toluenesulfonate tris (pt)
ont salts such as ert-butoxyphenyl) sulfonium, bis (benzenesulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (n-butylsulfonyl) diazomethane, bis (iso-butylsulfonyl). Diazomethane, bis (sec-butylsulfonyl) diazomethane, bis (n-propylsulfonyl)
Diazomethane derivatives such as diazomethane, bis (iso-propylsulfonyl) diazomethane and bis (tert-butylsulfonyl) diazomethane 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 is excellent in the standing wave reducing effect, but by combining the two, it is possible to finely adjust the profile.

The amount of the acid generator added is preferably 0.5 to 15 parts, more preferably 1 part with respect to 100 parts of the base resin.
~ 8 parts. If it is less than 0.5 parts, the sensitivity may be poor, and if it is more than 15 parts, the resolution of the resist material may be deteriorated due to a decrease in the alkali dissolution rate. There is a case where the sex is deteriorated.

The base resin other than the cross-linked polymer compound of the component (B) of the component (F) has a weight average molecular weight of 3 having a repeating unit represented by the following general formula (10). Polymer compounds of 1,000 to 300,000 are preferably used.

Further, by blending the component (F), pattern size control and pattern shape control can be arbitrarily performed, which is advantageous.

[0123]

[Chemical 44]

In the above formula, R ¹ , R ² , R ⁴ , R ⁵ and R
⁶ has the same meaning as above, R ¹⁴ is an acid labile group different from the above formula (5), for example, a group represented by the above formula (6), a tert-alkyl group, a trialkylsilyl group,
And a ketoalkyl group.

Each of e and f is 0 or a positive number, and
f may be 0 at the same time, g is a positive number, and e +
f + g = 1. The composition ratio of these is 0 ≦ e / (e + f
+ G) ≦ 0.5, preferably 0.1 ≦ e / (e + f +
g) ≦ 0.4, 0 ≦ f / (e + f + g) ≦ 0.5, preferably 0 ≦ f / (e + f + g) ≦ 0.2, 0.4 ≦ g /
(E + f + g) ≦ 0.9, preferably 0.6 ≦ g / (e
+ F + g) ≦ 0.8. The ratio of e to the whole (e + f + g, and so on) exceeds 0.5, the ratio of f to the whole exceeds 0.5, and the ratio of g to the whole is 0.9.
If the ratio exceeds g or if the ratio of g to the whole is less than 0.4, the contrast of the alkali dissolution rate becomes small and the resolution may deteriorate. By appropriately selecting the values of e, f, and g within the above range, pattern size control and pattern shape control can be arbitrarily performed.

Such a polymer compound has a weight average molecular weight of 3,000 to 300,000, preferably 5,000.
It must be 0 to 30,000. If the weight average molecular weight is less than 3,000, the resist material will be inferior in heat resistance, and if it exceeds 300,000, the alkali solubility will be lowered and the resolution will be deteriorated.

Further, also in the base resin of the component (F), when the molecular weight distribution (Mw / Mn) is wide, there are low molecular weight and high molecular weight polymers, and when there are many low molecular weight polymers, heat resistance is high. When the amount of the high-molecular-weight polymer is large, it may be difficult to dissolve in an alkali, which may cause a skirting after the pattern formation. Therefore, as the pattern rule becomes finer, the influence of such a molecular weight and the molecular weight distribution is likely to become large. Therefore, in order to obtain a resist material suitable for a fine pattern dimension, the base resin has a molecular weight distribution of 1. 0
A narrow dispersion of about 2.5 to 1.0, especially 1.0 to 1.5 is preferable.

The blending ratio of the base resin of the component (F) and the base resin of the component (B) (crosslinked polymer compound) is preferably 0: 100 to 90:10 by weight. Especially, 0: 100 to 50:50 is preferable. When the blending amount of the base resin of the component (F) is larger than the above weight ratio, the desired effect of the base resin of the component (B) (crosslinked polymer compound) may not be obtained.

The resist composition of the present invention may further contain a dissolution control agent as the component (G), whereby the contrast can be improved. 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. The compound substituted at an average ratio of 0 to 100% is added.

The substitution ratio of the hydrogen atom of the phenolic hydroxyl group with the acid labile group is 0 mol% or more, preferably 30 mol% or more of the whole phenolic hydroxyl group on average,
The upper limit is 100 mol%, more preferably 80 mol%.

In this case, the phenolic hydroxyl group is 2
Examples of the compound having one or more compounds include the following formulas (i) to (xi)
Those represented by are preferred.

[0132]

[Chemical formula 45]

[0133]

[Chemical formula 46]

[0134]

[Chemical 47] (However, in the formula, R ⁵¹ and R ⁵² are each a hydrogen atom or a linear or branched alkyl group or alkenyl group having 1 to 8 carbon atoms, and R ⁵³ is a hydrogen atom or a linear chain having 1 to 8 carbon atoms. Linear or branched alkyl group or alkenyl group, or-
(R ⁵⁷⁾ is _h -COOH, is _{^{R 54 - (CH 2) i}} -
(I = 2 to 10), C6 to C10 arylene group, carbonyl group, sulfonyl group, oxygen atom or sulfur atom, R
⁵⁵ is an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, a carbonyl group, a sulfonyl group, an oxygen atom or a sulfur atom, and R ⁵⁶ 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,
⁵⁷ is a linear or branched alkylene group having 1 to 10 carbon atoms. In addition, j is an integer of 0 to 5, u and h are 0 or 1. s, t, s ', t', s ", and t" satisfy s + t = 8, s '+ t' = 5, s "+ t" = 4, respectively, and have at least one hydroxyl group in each phenyl skeleton It is such a number. α is the formula (viii), (ix)
It is the number which makes the molecular weight of the compound of 100-1,000. )

In the above formula, R ⁵¹ and R ⁵² are, for example, hydrogen atom, methyl group, ethyl group, butyl group, propyl group, ethynyl group, cyclohexyl group, and R ⁵³ is, for example, R
⁵¹ , the same as R ⁵² , or —COOH, —CH ₂
COOH and R ⁵⁴ are, for example, ethylene group, phenylene group, carbonyl group, sulfonyl group, oxygen atom, sulfur atom and the like, and R ⁵⁵ is, for example, methylene group or R ⁵⁴
Examples of R ⁵⁶ similar to the 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 groups represented by the above general formulas (5) and (6), and t
Examples thereof include an ert-alkyl group, a trialkylsilyl group and a β-ketoalkyl group.

The compounding amount (dissolution controlling agent) in which the phenolic hydroxyl group is partially substituted with an acid labile group is 0 to 50 parts, preferably 5 to 50 parts, relative to 100 parts of the base resin.
Parts, more preferably 10 to 30 parts, and may be used alone or in admixture of two or more. If the content is less than 5 parts, the resolution may not be improved, and if it exceeds 50 parts, the pattern film may be reduced and the resolution may be deteriorated.

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

The resist composition of the present invention has a weight average molecular weight of more than 1,000 and not more than 3,000 as a separate dissolution control agent instead of or in addition to the above dissolution control agent, and has a phenolic hydroxyl group in the molecule. A compound in which the hydrogen atom of the phenolic hydroxyl group of the compound having is partially substituted with an acid labile group at an average of 0% or more and 60% or less can be blended.

In this case, as the compound in which the hydrogen atom of the phenolic hydroxyl group is partially substituted by such an acid labile group,
One or more compounds selected from the compounds having a repeating unit represented by the following general formula (11) and having a weight average molecular weight of more than 1,000 and 3,000 or less are preferable.

[0141]

[Chemical 48] (However, in the formula, R represents an acid labile group, and v and w are numbers satisfying 0 ≦ v / (v + w) ≦ 0.6, respectively.)

Here, the acid labile group of the dissolution control agent is a group represented by the general formula (5), a group represented by the general formula (6), a tert-alkyl group, a trialkylsilyl group, Examples thereof include a ketoalkyl group.

The amount of the above-mentioned other dissolution control agent 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, and preferably 1 to 0 parts
The range is preferably such that more than one part is used.

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

As the basic compound as the component (D), a compound which can suppress the diffusion rate when the acid generated from the acid generator diffuses in the resist film is suitable. By blending, the acid diffusion rate in the resist film is suppressed to improve resolution, suppress sensitivity change after exposure, reduce substrate and environment dependency, and improve exposure margin and pattern profile. be able to.

Examples of such basic compounds 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 a nitrogen-containing compound having a hydroxy group, a nitrogen-containing compound having a hydroxyphenyl group, an alcoholic nitrogen-containing compound, an amide derivative and an imide derivative, and an aliphatic amine is particularly preferably used.

Specifically, as the primary aliphatic amines, ammonia, methylamine, ethylamine, n-propylamine, iso-propylamine, n-butylamine, iso-butylamine, sec-butylamine,
tert-butylamine, pentylamine, tert-
Amylamine, cyclopentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine, nonylamine, decylamine, dodecylamine, cetylamine, methylenediamine, ethylenediamine, tetraethylenepentamine, etc. are exemplified, and as secondary aliphatic amines, Dimethylamine, diethylamine, di-n-propylamine, di-iso-propylamine, di-n-butylamine, di-iso-butylamine, di-sec-butylamine, dipentylamine, dicyclopentylamine, dihexylamine, dicyclohexylamine, Diheptylamine, dioctylamine,
Dinonylamine, didecylamine, didodecylamine,
Dicetylamine, N, N-dimethylmethylenediamine,
N, N-dimethylethylenediamine, N, N-dimethyltetraethylenepentamine and the like are exemplified, and as tertiary aliphatic amines, trimethylamine, triethylamine, tri-n-propylamine, tri-iso-propylamine, tri -N-butylamine, tri-iso-butylamine, tri-sec-butylamine, tripentylamine, tricyclopentylamine, trihexylamine, tricyclohexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, tri Dodecylamine, tricetylamine,
N, N, N ', N'-tetramethylmethylenediamine,
N, N, N ', N'-tetramethylethylenediamine,
N, N, N ', N'-tetramethyl tetraethylene pentamine etc. are illustrated.

Examples of the mixed amines include dimethylethylamine, methylethylpropylamine, benzylamine, phenethylamine, benzyldimethylamine and the like. Specific examples of aromatic 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, etc.), diphenyl (p-tolyl) amine, methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, pyrrole derivatives (eg pyrrole, 2H-pyrrole, 1-methyl). Pyrrole, 2,4-dimethylpyrrole, 2,5-dimethylpyrrole, N-methylpyrrole, etc.), oxazole derivative (eg, oxazole, isoxazole, etc.), thiazole derivative (eg, thiazole, isothiazole, etc.), imidazo Le derivative (such as imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, etc.), pyrazole derivatives, furazan derivatives, pyrroline derivatives (e.g. pyrroline, 2-methyl-1
-Pyrroline etc.), pyrrolidine derivative (e.g. pyrrolidine, N-methylpyrrolidine, pyrrolidinone, N-methylpyrrolidone etc.), imidazoline derivative, imidazolidine derivative, pyridine derivative (e.g. pyridine, methylpyridine, ethylpyridine, propylpyridine, butylpyridine, 4- (1-butylpentyl) pyridine, dimethylpyridine, trimethylpyridine, triethylpyridine,
Phenylpyridine, 3-methyl-2-phenylpyridine, 4-tert-butylpyridine, diphenylpyridine, benzylpyridine, methoxypyridine, butoxypyridine, dimethoxypyridine, 1-methyl-2-pyridone, 4-pyrrolidinipyridine, 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 (for example, quinoline, 3-quinolinecarbonitrile, etc.), isoquinoline derivative, cinnoline derivative, quinazoline derivative, quinoxaline derivative, phthalazine derivative, Purine derivatives, pteridine derivatives, carbazole derivatives, phenanthridine derivatives, acridine derivatives, phenazine derivatives, 1,10
-Phenanthroline derivative, adenine derivative, adenosine derivative, guanine derivative, guanosine derivative, uracil derivative, uridine derivative and the like are exemplified.

Further, examples of the nitrogen-containing compound having a carboxy group include aminobenzoic acid, indolecarboxylic acid, amino acid derivatives (for example, 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, P-toluenesulfonic acid pyridinium and the like are exemplified, and as the nitrogen-containing compound having a hydroxy group, the nitrogen-containing compound having a hydroxyphenyl group, and the alcoholic nitrogen-containing compound, 2-hydroxypyridine, aminocresol, 2,4-quinolinediol, 3-indole methanol hydrate, triethanolamine, N-ethyldiethanolamine, N,
N-diethylethanolamine, triisopropanolamine, 2,2'-iminodiethanol, 2-aminoethanol, 3-amino-1-propanol, 4-amino-1-butanol, 4- (2-hydroxyethyl) morpholine, 2- (2-hydroxyethyl) pyridine, 1-
(2-hydroxyethyl) piperazine, 1- [2- (2
-Hydroxyethoxy) ethyl] piperazine, piperidine ethanol, 1- (2-hydroxyethyl) pyrrolidine, 1- (2-hydroxyethyl) -2-pyrrolidinone, 3-piperidino-1,2-propanediol, 3-
Pyrrolidino-1,2-propanediol, 8-hydroxyurolidine, 3-cuinclidinol, 3-tropanol, 1-methyl-2-pyrrolidineethanol, 1-aziridineethanol, N- (2-hydroxyethyl) phthalimide, N- (2-hydroxyethyl) isonicotinamide etc. are illustrated. Examples of the amide derivative include formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide and the like. Examples of the imide derivative include phthalimide, succinimide, and maleimide. Especially triethylamine, N, N-dimethylaniline, N-methylpyrrolidone, pyridine, quinoline,
Nicotinic acid, triethanolamine, piperidine ethanol, N, N-dimethylacetamide, succinimide and the like are preferable.

The above basic compounds may be used alone or in combination of two or more, and the compounding amount thereof is 0.01 to 2 parts, particularly 0.01 to 100 parts with respect to 100 parts of the base resin. A mixture of 1 part is preferred. If the blending amount is less than 0.01 part, the blending effect may not be obtained, and if it exceeds 2 parts, the sensitivity may be lowered too much.

Further, the aromatic compound having a group represented by ≡C-COOH in the molecule to be incorporated as the component (E) in the resist material of the present invention is, for example, one kind selected from the following group I and group II. Alternatively, two or more compounds can be used, but the invention is not limited thereto. (E)
By blending the components, the PED stability of the resist can be improved and the edge roughness on the nitride film substrate can be improved. [Group I] A part or all of the hydrogen atoms of the phenolic hydroxyl group of the compounds represented by the following general formulas (12) to (21) are-
R ⁵⁷ —COOH (R ⁵⁷ is a linear or branched alkylene group having 1 to 10 carbon atoms) and has a phenolic hydroxyl group C in the molecule and a group D represented by ≡C—COOH. A compound having a molar ratio of C / (C + D) = 0.1 to 1.0. [Group II] Compounds represented by the following general formulas (22) and (23).

[0152]

[Chemical 49]

[0153]

[Chemical 50] (However, in the formula, R ¹ is a hydrogen atom or a methyl group,
R ⁵¹ and R ⁵² are each a hydrogen atom or a linear or branched alkyl group or alkenyl group having 1 to 8 carbon atoms,
⁵³ is a hydrogen atom or a linear or branched alkyl or alkenyl group having 1 to 8 carbon atoms, or - (R ⁵⁷⁾ _h -CO
OR 'group (R' is a hydrogen atom or -R ⁵⁷ -COOH) is, the _{^{R 54 - (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 ⁵⁵ is an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, a carbonyl group, a sulfonyl group, an oxygen atom or a sulfur atom, and R ⁵⁶ is a hydrogen atom or 1 to 8 carbon atoms. A linear or branched alkyl group, an alkenyl group, a phenyl group or a naphthyl group each substituted with a hydroxyl group, R ⁵⁷ is a linear or branched alkylene group having 1 to 10 carbon atoms, and R ⁵⁸ is A hydrogen atom, a linear or branched alkyl group or alkenyl group having 1 to 8 carbon atoms, or a —R ⁵⁷ —COOH group. j is an integer of 0 to 5, u and h are 0 or 1. s1, t1, s
2, t2, s3, t3, s4, t4 are each s1 + t
1 = 8, s2 + t2 = 5, s3 + t3 = 4, s4 + t4
= 6 and has at least one hydroxyl group in each phenyl skeleton. β is a number of the compound of formula (17) having a weight average molecular weight of 1,000 to 5,000, and γ is the compound of formula (18) having a weight average molecular weight of 1,000.
The number is 0 to 10,000. )

[0154]

[Chemical 51] (R ⁵¹ , R ⁵² , R ⁵⁷ and h have the same meanings as described above.
5, t5 are numbers that satisfy s5 ≧ 0 and t5 ≧ 0 and satisfy s5 + t5 = 5. )

Specific examples of the component (E) include compounds represented by the following general formulas VIII-1 to 14 and IX-1 to 6, but not limited thereto.

[0156]

[Chemical 52]

[0157]

[Chemical 53]

[0158]

[Chemical 54] (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. )

[0159]

[Chemical 55]

The aromatic 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 aromatic compound having a group represented by ≡C-COOH in the molecule is 0.1 to 5 parts, more preferably 1 to 3 parts, relative to 100 parts of the base resin. If it is less than 0.1 parts, the effect of improving the bottoming and PED on the nitride film substrate may not be sufficiently obtained, and if it is more than 5 parts, the resolution of the resist material may deteriorate.

Further, the resist material of the present invention comprises (H)
A compound having a molar absorptivity at a wavelength of 248 nm of 10,000 or less can be blended as a component ultraviolet absorber. This makes it possible to design and control a resist having an appropriate transmittance for substrates having different reflectances.

Specifically, pentalene, indene, naphthalene, azulene, peptalene, biphenylene, indacene, fluorene, phenalene, phenanthrene, anthracene, fluoranthene, acephenanthrylene, aceanthrylene, triphenylene, pyrene, chrysene,
Naphthalene, pleiaden, picene, perylene, pentaphene, pentacene, benzophenanthrene, anthraquinone, anthronebenzanthrone, 2,7-dimethoxynaphthalene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-dimethylanthracene, 9- Ethoxyanthracene, 1,2-naphthoquinone, 9-fluorene, condensed polycyclic hydrocarbon derivatives such as the following general formulas (24) and (25), condensed heterocyclic derivatives such as thioxanthen-9-one, thianthrene and dibenzothiophene, Two
3,4-tribitroxybenzophenone, 2,3,4
4'-tetrahydroxybenzophenone, 2,4-dihydroxybenzophenone, 3,5-dihydroxybenzophenone, 4,4'-dihydroxybenzophenone,
Examples thereof include benzophenone derivatives such as 4,4′-bis (dimethylamino) benzophenone and square acid derivatives such as square acid and dimethyl squarate.

[0164]

[Chemical 56] (In the formula, R⁶¹~ R⁶³Are independently hydrogen atom and straight chain
Or branched alkyl group, linear or branched
Alkoxy group, linear or branched alkoxyal
Kill group, linear or branched alkenyl group, or ari
Group. R ⁶⁴Is an optionally substituted oxygen atom
Or an unsubstituted divalent aliphatic hydrocarbon group, an oxygen atom
Substituted or unsubstituted divalent alicyclic carbon which may be contained
Hydrogen hydride group, optionally substituted or non-containing oxygen atom
A substituted divalent aromatic hydrocarbon group or an oxygen atom, R
⁶⁵Is an acid labile group. J is 0 or 1. E, F,
G is 0 or an integer of 1 to 9, respectively, and H is a positive value of 1 to 10.
It is an integer and satisfies E + F + G + H ≦ 10. )

More specifically, the above formulas (24) and (25)
Wherein R ^{61 to} R ⁶³ are each independently a hydrogen atom, a linear or branched alkyl group, a linear or branched alkoxy group, a linear or branched alkoxyalkyl group, a linear or branched Examples of the linear or branched alkyl group that is a linear alkenyl group or an aryl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a ter group.
Those having 1 to 10 carbon atoms such as t-butyl group, hexyl group, cyclohexyl group and adamantyl group are preferred, and among them, methyl group, ethyl group, isopropyl group and tert-butyl group are more preferably used. Examples of the linear or branched alkoxy group include carbon such as methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, hexyloxy group and cyclohexyloxy group. Those having a number of 1 to 8 are preferable, and among them, a methoxy group, an ethoxy group, an isopropoxy group, and a tert-butoxy group are more preferably used. As the linear or branched alkoxyalkyl group, those having 2 to 10 carbon atoms such as methoxymethyl group, ethoxypropyl group, propoxyethyl group and tert-butoxyethyl group are preferable, and among them, methoxymethyl group, Methoxyethyl group, ethoxypropyl group,
A propoxyethyl group and the like are preferable. As the linear or branched alkenyl group, those having 2 to 4 carbon atoms such as vinyl group, propenyl group, allyl group and butenyl group are preferable. As the aryl group, a phenyl group, a xylyl group,
Those having 6 to 14 carbon atoms such as a toluyl group and a cumenyl group are preferable.

R ⁶⁴ is a substituted or unsubstituted divalent aliphatic hydrocarbon group which may contain an oxygen atom, or a substituted or unsubstituted divalent alicyclic hydrocarbon group which may contain an oxygen atom. , A substituted or unsubstituted divalent aromatic hydrocarbon group which may contain an oxygen atom, or an oxygen atom. In the formula, J is 0 or 1, and when J is 0, -R ⁶⁴
-The bond is a single bond.

Examples of the substituted or unsubstituted divalent aliphatic hydrocarbon group which may contain an oxygen atom include methylene group, ethylene group, n-propylene group, isopropylene group, n-butylene group and sec- butylene group, -CH ₂
O- group, -CH ₂ CH ₂ O- group, -CH ₂ OCH ₂ - is preferred has 1 to 10 carbon atoms, such as radicals, among them methylene group, an ethylene group, -CH ₂ O- group, - CH ₂ CH ₂ O-
Groups are more preferably used.

Examples of the substituted or unsubstituted divalent alicyclic hydrocarbon group which may contain an oxygen atom include 1,
4-cyclohexylene group, 2-oxacyclohexane-
1,4-ylene group, 2-thiacyclohexane-1,4-
Examples thereof include those having 5 to 10 carbon atoms such as an ylene group.

As the substituted or unsubstituted divalent aromatic hydrocarbon group which may contain an oxygen atom, for example, o-
Phenylene group, p-phenylene group, 1,2-xylene-
3,6-ylene group, toluene-2,5-ylene group, 1-
Those having 6 to 14 carbon atoms, such as cumene-2,5-ylene group, or -CH ₂ Ph- group, -CH ₂ PhCH ₂ -
Groups, -OCH ₂ Ph- group, -OCH ₂ PhCH ₂ O- group (Ph is a phenylene group) allyl alkylene group having 6 to 14 carbon atoms such as.

R ⁶⁵ is an acid labile group, and the acid labile group as used herein means a group in which a carboxyl group is substituted with one or more functional groups capable of decomposing in the presence of an acid, It is not particularly limited as long as it decomposes in the presence of an acid to liberate a functional group showing alkali solubility. In particular, groups represented by the following general formulas (26a), (26b) and (26c) are preferable.

[0171]

[Chemical 57] (In the formula, R ^{66 to} R ⁶⁹ are each independently a hydrogen atom, a linear or branched alkyl group, a linear or branched alkoxy group, a linear or branched alkoxyalkyl group, or a linear Or, it is a branched alkenyl group or aryl group, and these groups may contain a carbonyl group in the chain, but not all of R ^{66 to} R ⁶⁹ are hydrogen atoms. ⁶⁶ and R ⁶⁷ may combine with each other to form a ring, and R ⁶⁹ represents a linear or branched alkyl group, a linear or branched alkoxyalkyl group, a linear or branched alkenyl. A group or an aryl group, and these groups may have a carbonyl group in the chain, and R ⁶⁹ may combine with R ⁶⁶ to form a ring.)

In this case, the above linear or branched alkyl group, linear or branched alkoxy group, linear or branched alkoxyalkyl group, linear or branched alkenyl group, aryl group As the above, the same as the above R ^{61 to} R ⁶³ can be exemplified.

The ring formed by combining R ⁶⁶ and R ⁶⁷ in the formula (26a) is, for example, a cyclohexylidene group, a cyclopentylidene group, a 3-oxocyclohexylidene group, a 3-oxo- group. 4-Oxacyclohexylidene group, a 4-methylcyclohexylidene group, etc. are mentioned.

The ring formed by combining R ⁶⁶ and R ⁶⁷ with each other in the formula (26b) is, for example, 1-silacyclohexylidene group, 1-silacyclopentylidene group, 3-oxo-1- Silacyclopentylidene group, 4-
Methyl-1-silacyclopentylidene group and the like having 3 to 3 carbon atoms
9 can be mentioned.

Further, in the formula (26c), the ring formed by R ⁶⁹ and R ⁶⁶ to be bonded to each other is, for example, a 2-oxacyclohexylidene group, a 2-oxacyclopentylidene group or a 2-oxa-4-. Examples thereof include those having 4 to 10 carbon atoms such as a methylcyclohexylidene group.

Examples of the group represented by the above formula (26a) include a tert-amyl group, a 1,1-dimethylethyl group, a 1,1-dimethylbutyl group, and a 1-ethyl-group.
In addition to tertiary alkyl groups having 4 to 10 carbon atoms such as 1-methylpropyl group and 1,1-diethylpropyl group, 1,1-
A 3-oxoalkyl group such as a dimethyl-3-oxobutyl group, a 3-oxocyclohexyl group, a 1-methyl-3-oxo-4-oxacyclohexyl group is preferable.

Examples of the group represented by the above formula (26b) include trialkylsilyl groups having 3 to 10 carbon atoms such as trimethylsilyl group, ethyldimethylsilyl group, dimethylpropylsilyl group, diethylmethylsilyl group and triethylsilyl group. It is suitable.

Examples of the group represented by the above formula (26c) include 1-methoxymethyl group, 1-methoxyethyl group, 1-ethoxyethyl group, 1-ethoxypropyl group,
1-ethoxyisobutyl group, 1-n-propoxyethyl group, 1-tert-butoxyethyl group, 1-n-butoxyethyl group, 1-iso-butoxyethyl group, 1-te
rt-pentoxyethyl group, 1-cyclohexyloxyethyl group, 1- (2'-n-butoxyethoxy) ethyl group, 1- (2'-ethylhexyl) oxyethyl group, 1
-(4'-acetoxymethylcyclohexylmethyloxy) ethyl group, 1- {4 '-(tert-butoxycarbonyloxymethyl) cyclohexylmethyloxy} ethyl group, 2-methoxy-2-propyl group, 1-ethoxypropyl group, A dimethoxymethyl group, a diethoxymethyl group, a tetrahydrofuranyl group, a tetrahydropyranyl group and the like having 2 to 8 carbon atoms are preferable.

In the above formulas (24) and (25), E, F and G are 0 or a positive integer of 1 to 9, respectively, and H
Is a positive integer of 1 to 10 and satisfies E + F + G + H ≦ 10.

Preferred specific examples of the compounds of the above formulas (24) and (25) include compounds represented by the following (27a) to (27j).

[0181]

[Chemical 58] (In the formula, R ⁷⁰ is an acid labile group.)

As the ultraviolet absorber, bis (4-
Hydroxyphenyl) sulfoxide, bis (4-ter
t-butoxyphenyl) sulfoxide, bis (4-te
Diaryl sulfoxide derivatives such as rt-butoxycarbonyloxyphenyl) sulfoxide and bis [4- (1-ethoxyethoxy) phenyl] sulfoxide, bis (4-hydroxyphenyl) sulfone, bis (4-te)
rt-butoxyphenyl) sulfone, bis (4-ter)
t-butoxycarbonyloxyphenyl) sulfone, bis [4- (1-ethoxyethoxy) phenyl] sulfone, bis [4- (1-ethoxypropoxy) phenyl]
Diaryl sulfone derivatives such as sulfone, benzoquinone diazide, naphthoquinone diazide, anthraquinone diazide, diazofluorene, diazotetralone, diazo compounds such as diazophenanthrone, naphthoquinone-1,2
-Complete or partial ester compounds of diazide-5-sulfonic acid chloride and 2,3,4-trihydroxybenzophenone, naphthoquinone-1,2-diazide-4-sulfonic acid chloride and 2,4,4'-trihydroxybenzophenone It is also possible to use a quinonediazide group-containing compound such as a complete or partial ester compound of

As the ultraviolet absorber, tert-butyl 9-anthracenecarboxylate, tert-amyl 9-anthracenecarboxylate, tert-methoxymethyl 9-anthracenecarboxylate, tert-ethoxyethyl 9-anthracenecarboxylate, 9- Anthracenecarboxylic acid tert-tetrahydropyranyl, 9-anthracenecarboxylic acid tert-tetrahydrofuranyl,
Examples thereof include partial ester compounds of naphthoquinone-1,2-diazide-5-sulfonic acid chloride and 2,3,4-trihydroxybenzophenone.

The amount of the ultraviolet absorber as the component (H) blended is 0 to 10 parts, more preferably 0.5 to 10 parts, and still more preferably 1 to 5 parts, relative to 100 parts of the base resin. preferable.

Further, the resist material of the present invention comprises (I)
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 (28) and (29) can be preferably used.

[0187]

[Chemical 59] (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) and the like. Surfynol (Su
rfynol) is a manufacturer in the US AirProd
octs and Chemicals Inc. Is a trademark of

The addition amount of the above acetylene alcohol derivative 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, and examples thereof include perfluoroalkyl polyoxyethylene ethanol, fluorinated alkyl esters, perfluoroalkylamine oxides, and fluorine-containing organosiloxane compounds. For example, Florard "F
C-430 "," FC-431 "(all manufactured by Sumitomo 3M Limited), Surflon" S-141 "," S-1 "
45 "(all manufactured by Asahi Glass Co., Ltd.), Unidyne" DS
-401 "," DS-403 "," DS-451 "(all manufactured by Daikin Industries, Ltd.), Megafac" F-8 "
151 "(manufactured by Dainippon Ink and Machinery Co., Ltd.)," X-70- "
092 "," X-70-093 "(all manufactured by Shin-Etsu Chemical Co., Ltd.) and the like can be mentioned. Preferably, Florard “FC-430” (Sumitomo 3M Limited)
Manufactured 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 lay 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.

[0193]

Industrial Applicability The chemically amplified positive resist composition of the present invention is sensitive to high energy rays, is excellent in sensitivity, resolution and plasma etching resistance, and is also excellent in heat resistance and reproducibility of resist patterns. In addition, the pattern is unlikely to be overhanging and has excellent dimensional controllability. Furthermore, the storage stability is improved by blending the acetylene alcohol derivative. Therefore, the chemically amplified positive type resist material of the present invention can be a resist material having a small absorption particularly at the exposure wavelength of the KrF excimer laser due to these characteristics, and can easily form a fine pattern perpendicular to the substrate. Since it can be formed, it is suitable as a fine pattern forming material for VLSI manufacturing.

[0194]

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

[Synthesis Example 1] 100 g of polyhydroxystyrene was added to dimethylformamide (100) in a 2 L flask.
After dissolving in 0 ml and adding a catalytic amount of p-toluenesulfonic acid, 30 g of ethyl vinyl ether and 2 parts of triethylene glycol divinyl ether while stirring at 20 ° C.
g was added. After reacting for 1 hour, the mixture was neutralized with concentrated aqueous ammonia, and the neutralization reaction solution was added dropwise to 10 L of water to obtain a white solid. After filtering this, acetone 50
It was dissolved in 0 ml, added dropwise to 10 L of water, filtered, and vacuum dried. It was confirmed from ¹ H-NMR that 27% of the hydrogen atoms of the hydroxyl groups of polyhydroxystyrene were ethoxyethylated and 3% of the obtained polymer was crosslinked (P
olym. 1).

[Synthesis Example 2] 100 g of polyhydroxystyrene was added to 100 ml of dimethylformamide in a 2 L flask.
After dissolving in 0 ml and adding a catalytic amount of p-toluenesulfonic acid, 30 g of ethyl vinyl ether and 2 g of 1,4-di (vinyl ether) cyclohexane were 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 10 L of water to obtain a white solid. After filtering this, acetone 5
It was dissolved in 00 ml, added dropwise to 10 L of water, filtered, and vacuum dried. It was confirmed by ¹ H-NMR that the hydrogen atoms of the hydroxyl groups of polyhydroxystyrene of the obtained polymer were 27% ethoxyethylated and 3% were crosslinked.

Further, 50 g of the resulting partially crosslinked ethoxyethoxylated polyhydroxystyrene was added to pyridine 5
Dissolve in 00 ml and stir at 45 ° C with dicarbonic acid di-
7 g of tert-butyl was added. After reacting for 1 hour, the reaction solution was added dropwise to 3 L of water to obtain a white solid. This was filtered, dissolved in 50 ml of acetone, added dropwise to 2 L of water, filtered, and vacuum dried to obtain a polymer. The obtained polymer has the following rational formula (Polym. 2).
According to ¹ H-NMR, the ethoxyethylation rate of the hydrogen atom of the hydroxyl group of polyhydroxystyrene was 27%, and the tert-butoxycarbonylation rate of the hydrogen atom of the hydroxyl group was 8%.

[Synthesis Example 3] 50 g of polyhydroxystyrene was added to 500 ml of dimethylformamide in a 2 L flask.
And a catalytic amount of p-toluenesulfonic acid was added thereto, and the mixture was stirred at 20 ° C. with ethyl vinyl ether 27
g, 1,4-di (vinyl ether) cyclohexane 3 g
Was added. After reacting for 1 hour, the mixture was neutralized with concentrated aqueous ammonia, and the neutralization reaction solution was added dropwise to 10 L of water.
A white solid was obtained. After filtering this, 500m of acetone
It was dissolved in 1 l, added dropwise to 10 L of water, filtered, and dried in vacuum. It was confirmed from ¹ H-NMR that the hydrogen atom of the hydroxyl group of polyhydroxystyrene was 24% ethoxyethylated and 10% was crosslinked in the obtained polymer (Po.
lym. 3).

[Synthesis Examples 4 to 7] Polymers represented by the following rational formulas (Polym. 4 to 7) were obtained by the same method as in Synthesis Examples 1 to 3.

[Synthesis Example 8] 100 g of polyhydroxystyrene was dissolved in 900 g of tetrahydrofuran in a 2 L flask, 3.9 g of methanesulfonic acid was added, and then 3
Ethyl 1-propenyl ether 2 with stirring at 0 ° C
8.2g was added and it was made to react for 3 hours. Then 1,4
-Adding 3.8 g of butanediol divinyl ether,
After reacting for 0.5 hour, the mixture was neutralized with concentrated aqueous ammonia. The reaction solution was subjected to solvent exchange with ethyl acetate, purified water and a small amount of acetone were used for 6 liquid separation purifications, and then the solvent was exchanged with acetone and added dropwise to 20 L of pure water to obtain a white solid. This is filtered, washed twice with pure water, filtered,
Vacuum dried. The obtained polymer has the following rational formula (Pol
ym. It has a structure shown in 8), and it was confirmed from ¹ H-NMR that hydrogen atoms of hydroxyl groups of polyhydroxystyrene were 26% ethoxypropoxylated and 5.5% were crosslinked.

[Synthesis Example 9] In a 2 L flask, 100 g of polyhydroxystyrene was dissolved in 900 g of tetrahydrofuran, and 3.9 g of methanesulfonic acid was added.
Ethyl 1-propenyl ether 2 with stirring at 0 ° C
After adding 0.0 g and reacting for 3 hours, 3.8 g of 1,4-butanediol divinyl ether was added. 0.
After reacting for 5 hours, the mixture was neutralized with concentrated aqueous ammonia. The reaction solution was subjected to solvent exchange with ethyl acetate, purified water and a small amount of acetone were used for 6 liquid separation purifications, and then the solvent was exchanged with acetone and added dropwise to 20 L of pure water to obtain a white solid. This is filtered, washed twice with pure water, filtered,
Vacuum dried.

Further, 50 g of the partially crosslinked ethoxypropoxylated polyhydroxystyrene thus obtained was dissolved in 300 g of pyridine and the mixture was stirred at 40.degree.
4.5 g of tert-butyl was added. After reacting for 1 hour, the reaction solution was added dropwise to 10 L of water to obtain a white solid. This was filtered, dissolved in 200 ml of acetone, added dropwise to 2 L of water, filtered, and vacuum dried to obtain a polymer. The obtained polymer has the following rational formula (Polym.
9H has a structure shown in 9), and from ¹ H-NMR, the hydrogen atom of the hydroxyl group of polyhydroxystyrene was 21% ethoxypropoxylated, 5% was tert-butoxycarbonylated, and 5.5% was crosslinked. Was confirmed.

[Synthesis Example 10] Polyhydroxystyrene (100 g) and tetrahydrofuran (900 g) were placed in a 2 L flask.
And 3.9 g of methanesulfonic acid were added,
24.0 g of ethyl vinyl ether with stirring at 30 ° C
Was added and reacted for 1 hour. Next, 3.8 g of 1,4-butanediol divinyl ether was added, and the mixture was reacted for 0.5 hour and then neutralized with concentrated aqueous ammonia. The reaction solution was solvent-exchanged with ethyl acetate and purified by pure water 6 times, then the solvent was exchanged with acetone and added dropwise to 20 L of pure water to obtain a white solid. This was filtered, washed twice with pure water, filtered, and dried in vacuum. The resulting polymer has a structure represented by the following rational formula (Polym.10), and from ¹ H-NMR, the hydrogen atom of the hydroxyl group of polyhydroxystyrene was 31% ethoxyethylated and 5.5% was crosslinked. It was confirmed that

[Synthesis Example 11] 100 g of polyhydroxystyrene was added to 900 g of tetrahydrofuran in a 2 L flask.
And 3.9 g of methanesulfonic acid were added,
16.4 g of ethyl vinyl ether with stirring at 30 ° C
Was added and reacted for 1 hour. After adding 3.8 g of 1,4-butanediol divinyl ether and reacting for 0.5 hour, the mixture was neutralized with concentrated aqueous ammonia. The reaction solution was solvent-exchanged with ethyl acetate, purified by pure water 6 times, and then purified.
When the solvent was exchanged with acetone and 20 L of pure water was added dropwise, a white solid was obtained. This was filtered, washed twice with pure water, filtered, and dried in vacuum.

Further, 50 g of the partially crosslinked ethoxyethoxylated polyhydroxystyrene obtained was mixed with pyridine 3
Dissolve in 00g and stir at 40 ° C with dicarbonic acid di-t.
4.5 g of ert-butyl was added. After reacting for 1 hour, the reaction solution was added dropwise to 10 L of water to obtain a white solid. This was filtered, dissolved in 200 ml of acetone, added dropwise to 2 L of water, filtered, and vacuum dried to obtain a polymer. The obtained polymer has the following rational formula (Polym.
Has a structure represented by 11), ¹ H-NMR hydrogen atoms of hydroxyl groups of polyhydroxystyrene are 18.0% ethoxyethoxy of from 5% is tert- butoxycarbonyl reduction, 5.5% cross-linked It was confirmed that

[Synthesis Example 12] A polymer represented by the following rational formula (Polym. 12) was obtained by the same method as in Synthesis Example 11 except that ethyl vinyl ether was not used.

[Synthesis Example 13] Poly (3,4-dihydroxystyrene) and alkenyl ether compound (I-22)
In the same manner as in Synthesis Example 11 using the following rational formula (P
olym. A polymer represented by 13) was obtained.

[Synthesis Example 14] A polymer represented by the following rational formula (Polym.14) was obtained by the same method as in Synthesis Example 9 using the alkenyl ether compound (II-1).

The structure of the obtained polymer was as shown in the following rational formula, and the respective substitution rates were as shown in Table 1. In the formula below, R is the unit U1 or U2 below.
Represents a cross-linking group that is intermolecularly or intramolecularly crosslinked with (R)
Indicates a state in which the bridging group R is bonded.

[0210]

[Chemical 60]

[0211]

[Chemical formula 61]

[0212]

[Chemical formula 62]

[0213]

[Chemical formula 63]

[0214]

[Chemical 64]

[0215]

[Chemical 65]

[0216]

[Chemical formula 66]

[0217]

[Chemical formula 67]

[0218]

[Chemical 68]

[0219]

[Table 1] * Polyhydroxystyrene

[Examples and Comparative Examples] The polymer compounds (Polym. 1 to 14) obtained in the above synthesis examples were used as base resins,
Acid generator represented by the following formula (PAG.1-12), dissolution controller represented by the following formula (DRR.1-4), basic compound, intramolecular represented by the following formula (ACC.1, 2) To ≡
A resist material component selected from an aromatic compound having a group represented by C-COOH and an ultraviolet absorber represented by the following formula (DYE.1, 2) is dissolved in a solvent to prepare a resist composition as shown in Tables 2 and 3. The liquid was prepared. If necessary, the surfactant Florard “FC-430 (Sumitomo 3M Limited)
Manufactured) was added to improve the film forming property.

For comparison, the following rational expression (Poly
m. 15 to 18) was used as a base resin to prepare a resist solution having the composition shown in Table 4 in the same manner as above.

A resist solution was prepared by filtering each of these compositions through a 0.1 μm Teflon (registered trademark) filter. This was spin-coated on a silicon wafer, and this silicon wafer was baked on a hot plate at 100 ° C. for 90 seconds. The film thickness is 0.5
It was set to 5 μm.

Then, it is exposed using an excimer laser stepper (NSR-2005EX NA = 0.5, Nikon Corporation) through a mask for forming a desired pattern, baked at 110 ° C. for 90 seconds, and 2. 60% with 38% tetramethylammonium hydroxide in water
When development was performed for a second, a positive type pattern could be obtained.

The obtained resist pattern was evaluated as follows. First, the sensitivity (Eth) was determined. Then 0.24
1: 1 top and bottom of μm line and space
The exposure amount resolved in step 1 was taken as the optimum exposure amount (sensitivity: Eop), and the minimum line width of separated lines and spaces in this exposure amount was taken as the resolution of the evaluation resist. The resolution was also observed when the time lapse (PED) from the exposure with the same exposure amount to the heat treatment was 2 hours. In addition, the shape of the resolved resist pattern was observed using a scanning electron microscope, and this resist pattern was examined by a heat resistance test.
The sample was heated on a hot plate at 0 ° C. for 10 minutes, and changes in the pattern shape before and after heating were observed.

The resist compositions are shown in Tables 2 to 4, the evaluation results of Examples are shown in Table 5, and the evaluation results of Comparative Examples are shown in Table 6.

[0226]

[Chemical 69]

[0227]

[Chemical 70]

[0228]

[Chemical 71]

[0229]

[Chemical 72]

[0230]

[Chemical formula 73]

[0231]

[Chemical 74]

[0232]

[Chemical 75]

[0233]

[Chemical 76]

[0234]

[Table 2]

[0235]

[Table 3]

[0236]

[Table 4] DGLM: 2-methoxyethyl ether EIPA: 1-ethoxy-2-propanol EL / BA: mixed solution of ethyl lactate (85% by weight) and butyl acetate (15% by weight) PGMEA: propylene glycol monomethyl ether acetate PGMEA / EP: propylene Mixed solution PGMEA / CH of glycol monomethyl ether acetate (90% by weight) and ethyl pyruvate (10% by weight): Propylene Mixed solution of glycol monomethyl ether acetate (90% by weight) and cyclohexanone (10% by weight) PGMEA / EL: Propylene Mixed solution of glycol monomethyl ether acetate (70% by weight) and ethyl lactate (30% by weight)

[0237]

[Table 5] Heat resistance ○: No change in pattern shape before and after heating

[0238]

[Table 6] Heat resistance ○: No change in pattern shape before and after heating ×: Pattern deterioration due to heat dripping after heating

Next, the above-mentioned Examples 21, 22, 23 and 24.
The resist composition of
The storage stability of the resist composition containing 0.05% by weight of the total amount was examined with respect to an increase in particles (foreign matter). The results are shown in Table 7 below. On this occasion,
KL-20A (manufactured by Rion Co., Ltd.) was used as a submerged particle counter, and the particle size of 0.3 μm in the accelerated test by storage at 40 ° C. was monitored.

[0240]

[Chemical 77]

[0241]

[Table 7]

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor ▲ Flag ▼ Chikin 1 Hitomi, Osamu, Matsuida-cho, Usui-gun, Gunma 10 Shin-Etsu Chemical Co., Ltd. Silicon Electronic Materials Research Laboratory (72) Inventor Yoshifumi Takeda Niigata 28-1 Nishi-Fukushima, Chubiki-mura, Nakakubiki-gun, Shinagawa Prefecture, Shin-Etsu Chemical Co., Ltd.Synthesis Technology Research Institute (72) Inventor Shigehiro Nagura 28-1, Nishi-Fukushima, Kubiki-mura, Naka-Kubiki-gun, Niigata Shin-Etsu Chemical Co., Ltd. (72) Inventor Toshinobu Ishihara 28-1 Nishikofukushima, Kubiki-mura, Nakakubiki-gun, Niigata Prefectural Shinetsu Chemical Industry Co., Ltd.Synthesis Technology Research Laboratory (72) Inventor Ao Yamaoka 3-22-7 Motonakayama, Funabashi, Chiba (56) References JP-A-8-253534 (JP, A) JP-A-8-305025 (JP, A) JP-A-5-181279 (JP, A) JP-A-8-15864 ( P, A) JP 7-92679 (JP, A) JP 8-262721 (JP, A) JP 8-160622 (JP, A) JP 7-333834 (JP, A) JP Hei 7-319163 (JP, A) JP 10-20504 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) G03F ^7/ 00-7/42

Claims (14)

(57) [Claims] 1. (A): Organic solvent (B): One or more types of acid labile as the base resin
The polymer compound having a group is further intramolecular and / or intermolecular
At a heavy chain which is cross-linked by a cross-linking group having a C-O-C group.
Polymerization with a weight average molecular weight of 1,000 to 500,000
Compound (C): Acid generator And the above-mentioned base resin has the following general formula (3)
Is represented by R of a polymer compound having a repeating unit represented by
The hydrogen atom of the phenolic hydroxyl group is removed and its oxygen
C- whose atom is represented by the following general formula (4a) or (4b)
Intramolecular and / or intermolecular due to a crosslinking group having an O—C group
The total amount of the acid labile group and the crosslinkable group
Is all hydrogen atoms of the phenolic hydroxyl group of the following general formula (1)
The proportion of the body is more than 0 mol% and less than 80 mol% on average.
And the weight average molecular weight is 1,000 to 500,000.
And R in the following formula (3)^FourAnd the following formula (4a)
Is R in (4b)⁸And R⁹And are different from each other
And R^FiveAnd R⁸And R⁹And are the same or different from each other
A chemical amplification positive characterized by being a polymer compound
Type resist material. [Chemical 1] (In the formula, R is a hydroxyl group or OR³Group, at least 1
The individual is a hydroxyl group. R¹Represents a hydrogen atom or a methyl group
And R²Is a straight-chain, branched or cyclic chain having 1 to 8 carbon atoms.
Indicates a rukyl group. R³Represents an acid labile group. R^Four, R^FiveIs
Hydrogen atom or linear, branched or cyclic having 1 to 8 carbon atoms
Represents an alkyl group, R⁶Is a hetero atom having 1 to 18 carbon atoms
Represents a monovalent hydrocarbon group which may have^FourWhen
R^Five, R^FourAnd R⁶, R ^FiveAnd R⁶And may form a ring,
To form R^Four, R^Five, R⁶Each has 1 carbon
18 linear or branched alkylene groups are shown. R⁷
Represents a tertiary alkyl group having 4 to 12 carbon atoms. Also, x is
0 or a positive integer, y is a positive integer and satisfies x + y ≦ 5
Is a number to add, k is 0 or a positive integer, m is 0 or a positive integer
Is an integer, n is a positive integer, and satisfies k + m + n ≦ 5
It is the number to add. p1 and p2 are positive numbers, q1 is a positive number, q2
Is 0 or a positive number, and 0 <p1 / (p1 + q1 + q2 +
p2) ≦ 0.8, 0 <q1 / (p1 + q1 + q2 + p
2) ≦ 0.8, 0 ≦ q2 / (p1 + q1 + q2 + p2)
≦ 0.8, a number that satisfies p1 + q1 + q2 + p2 = 1
is there. a is 0 or a positive integer of 1-6. x, y,
k, m and n have the same meanings as described above. ) [Chemical 2] (In the formula, R⁸, R⁹Is a hydrogen atom or a straight chain having 1 to 8 carbon atoms
Represents a cyclic, branched or cyclic alkyl group. Or R⁸When
R⁹And may form a ring, and when forming a ring,
R⁸, R⁹Is a straight-chain or branched alkylene having 1 to 8 carbon atoms.
Group. R¹³Is a straight or branched chain having 1 to 10 carbon atoms
Is an alkylene group, and d is 0 or an integer of 1 to 10. A
Is a saturated C 1 -C 50 aliphatic or alicyclic saturated
Represents a hydrocarbon group, an aromatic hydrocarbon group or a heterocyclic group,
These groups may have a heteroatom interposed, and
Some of the hydrogen atoms bonded to the carbon atoms of
Substituted by a xyl group, carbonyl group or fluorine atom
It may be. B is -CO-O-, -NHCO-O-
Or it shows -NHCONH-. c is 2 to 8 and c'is 1 to
It is an integer of 7. ) [Chemical 3] (In the formula, R¹Represents a hydrogen atom or a methyl group, R²Is carbon
Indicates a linear, branched or cyclic alkyl group of the number 1-8
You In addition, x is 0 or a positive integer, y is a positive integer,
It is a number that satisfies x + y ≦ 5. ) 2. The chemically amplified positive resist composition according to claim 1, wherein R ⁴ is an ethyl group and R ⁸ is a methyl group. 3. The chemically amplified positive resist composition according to claim 2, wherein R ⁵ and R ⁹ are each a hydrogen atom. 4. The chemically amplified positive resist composition according to claim 1, wherein —CR ⁴ R ⁵ —OR ⁶ is a hydropyranyl group, and R ⁸ is a methyl group. 5. The chemically amplified positive type resist material according to claim 1, wherein an onium salt and / or a diazomethane derivative is blended as the component (C). 6. The chemically amplified positive resist composition according to claim 1, wherein a basic compound is added as the component (D). 7. The chemically amplified positive resist composition according to claim 6, wherein an aliphatic amine is blended as the component (D). 8. A compound represented by the formula: 8. The chemically amplified positive resist composition according to claim 1, wherein an aromatic compound having a group represented by: is blended. 9. Further, as a base resin other than the component (F) :( B), one or more hydrogen atoms of a phenolic hydroxyl group of a polymer compound having a repeating unit represented by the following general formula (1) or A polymer compound having a weight average molecular weight of 3,000 to 300,000, which is partially substituted with two or more kinds of acid labile groups at a ratio of 0 mol% to 80 mol% on average as a whole. 9. The chemically amplified positive type resist material according to any one of 1 to 8. [Chemical 4] (In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² represents a linear, branched, or cyclic alkyl group having 1 to 8 carbon atoms. Further, x is 0 or a positive integer, and y is Is a positive integer,
It is a number that satisfies x + y ≦ 5. ) 10. The following general formula (1) is used as the component (F).
0) has a repeating unit represented by
3,000 to 300,000 polymer compounds were blended
10. The chemically amplified positive resist according to claim 9, wherein
Material. [Chemical 5] (In the formula, R¹, R², R^Four, R^Five, R⁶Has the same meaning as above
Indicates R¹⁴Is -CR^FourR ^FiveOR⁶Acid labile group different from
Where e and f are 0 or a positive number, g is a positive number, and e + f + g
= 1 and 0 ≦ e / (e + f + g) ≦ 0.5, 0.4
≦ g / (e + f + g) ≦ 0.9. ) 11. The chemically amplified positive resist material according to claim 1, further comprising (G): a dissolution control agent. 12. The chemically amplified positive type resist material according to claim 1, further comprising (H): an ultraviolet absorber. 13. The chemically amplified positive resist composition according to claim 1, further comprising (I): an acetylene alcohol derivative. 14. (i) Any one of claims 1 to 13
The step of applying the chemically amplified positive type resist material on the substrate according to the item (ii), followed by a heat treatment, and then exposing with a high energy beam or an electron beam having a wavelength of 300 nm or less through a photomask; 3.) A pattern forming method, which comprises a step of performing a heat treatment if necessary and then developing with a developing solution.