JP2002244299A - Chemically amplified positive resist material and pattern forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a chemically amplified positive resist material sensitive to high energy beams, excellent in sensitivity, resolution and plasma etching resistance and giving a resist pattern excellent in heat resistance and reproducibility. SOLUTION: The chemically amplified positive resist material contains (A) an organic solvent, (B) a high molecular compound having an acid labile group, crosslinked with a crosslinking group and having a weight average molecular weight of 1,000-500,000 as a base resin and (C) an acid generating agent. The base resin is obtained by reacting a high molecular compound of formula (1') with an alkenyl ether compound of formula (I) and a compound of formula (5a).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a polymer compound having one or more acid labile groups, wherein the compound is further intramolecularly and / or
Alternatively, by blending a polymer compound cross-linked by a cross-linking group having a C—O—C group between molecules into a resist material as a base resin, alkali dissolution contrast before and after exposure is significantly higher, and high sensitivity and high resolution are obtained. The present invention relates to a chemically amplified positive resist material having excellent image reproducibility, particularly as a fine pattern forming material for VLSI manufacturing.

[0002]

2. Description of the Related Art In recent years,
As the integration and speed of LSIs have been increased and the pattern rules have been required to be finer, far-ultraviolet lithography has been regarded as a promising next-generation fine processing technology. The deep ultraviolet lithography can process 0.5 μm or less, and when a resist material having low light absorption is used, a pattern having a side wall nearly perpendicular to the substrate can be formed.

A recently developed acid-catalyzed chemically amplified positive resist material (Japanese Patent Publication No. 2-27660,
Japanese Patent Application Laid-Open No. 3-27829) utilizes a high-intensity KrF excimer laser as a light source of far ultraviolet rays, and is particularly promising for far ultraviolet lithography having high sensitivity, high resolution, high dry etching resistance, and excellent characteristics. It is expected as a resist material.

As such a chemically amplified positive resist material, there are known 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 controller having an acid labile group. Have been.

For example, Japanese Patent Application Laid-Open No. 62-115440 discloses a resist material comprising poly-4-tert-butoxystyrene and an acid generator. Is a two-component resist material comprising a resin having a tert-butoxy group in the molecule and an acid generator.
No. 8 proposes a two-component resist material comprising a polyhydroxystyrene containing a methyl group, an isopropyl group, a tert-butyl group, a tetrahydropyranyl group and a trimethylsilyl group, and an acid generator.

Further, JP-A-6-100488 discloses 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 resin of these resist materials has an acid labile group in a side chain, and the acid labile group is decomposed by a strong acid such as a tert-butyl group and a tert-butoxycarbonyl group. As a result, it reacts with the basic compound in the air to deactivate, so that the decomposition of the acid labile group hardly occurs, and the pattern shape of the resist material tends to be a T-top shape. On the other hand, since alkoxyalkyl groups such as ethoxyethyl groups are decomposed by weak acids, the influence of basic compounds in the air is small, but the pattern shape becomes extremely thin with the passage of time from exposure to heat treatment. Or has a bulky group in the side chain, so that heat resistance is lowered, sensitivity and resolution are not satisfactory, and both have problems and have not yet been put to practical use At present, it is desirable to improve these problems.

The polymer compound disclosed in Japanese Patent Application Laid-Open No. Hei 8-305025 is aimed at improving the above-mentioned problem. It is difficult, and Japanese Patent Application Laid-Open No. 8-253534.
Has the disadvantage of inducing by-products of the cross-linking groups described in Japanese Patent Application Laid-Open No. H10-260, 1988. 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 the amount of addition, and further, reproducibility of the production of the polymer compound is required. However, the production method described in the above publication has a drawback that the selection of the acid labile group and the crosslinkable group and the ratio of the substituents must be restricted.

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

[0010]

Means for Solving the Problems and Embodiments of the Invention The present inventors have made intensive studies in order to achieve the above object, and as a result, the weight average molecular weight obtained by the method described below is 1,000 to 500,000. 1 cross-linked by a cross-linking group having a C—O—C group within a certain 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, an aromatic compound having a group represented by −C-COOH in the molecule. The chemically amplified positive resist material containing the compound enhances the dissolution contrast of the resist film, and particularly increases the dissolution rate after exposure.
Improving D stability, improving edge roughness on nitride film substrate, and blending acetylene alcohol derivative to improve coating properties and storage stability,
It has been found that it is excellent in high resolution, exposure latitude, process adaptability, high in practicability, and precise fine processing, and is very effective as a resist material for VLSI.

That is, the present invention provides the following chemically amplified positive resist material and a pattern forming method. Claim 1: (A): an organic solvent (B): a polymer compound having one or more acid labile groups as a base resin further has a C—O—C group within and / or between molecules. A polymer compound having a weight average molecular weight of 1,000 to 500,000 crosslinked by a crosslinking group (C): an acid generator, wherein the base resin is represented by the following general formula (1 ′) A polymer compound having a weight average molecular weight of 1,000 to 500,000 having a repeating unit represented by the following general formula (I) or (II) and a alkenyl ether compound represented by the following general formula (5a) A compound represented by the following general formula (3)
A chemically amplified positive resist material characterized by being a polymer compound represented by a'-1) and / or (3a'-2).

Embedded image

Embedded image(Where R¹Represents a hydrogen atom or a methyl group;^TwoIs carbon
Represents a linear, branched or cyclic alkyl group of the formulas 1 to 8
You. Further, x is 0 or a positive integer, y is a positive integer,
It is a number that satisfies x + y ≦ 5. R^Four, R^FiveIs a hydrogen atom or
Is a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms
And R⁶Has a heteroatom having 1 to 18 carbon atoms.
A monovalent hydrocarbon group which may be^FourAnd R^Five, R^FourWhen
R⁶, R^FiveAnd R⁶May form a ring or form a ring
R in case^Four, R^Five, R⁶Are straight-chains each having 1 to 18 carbon atoms.
It represents a chain or branched alkylene group. R^4aIs a hydrogen atom
Or a linear, branched or cyclic alkyl having 1 to 7 carbon atoms
A group represented by R^4a-CH and R^FiveOr R^{Four a}-CH and R⁶Is a ring
May be formed, and when forming a ring, R^4a-CH
Is R ^4a-CH_TwoR represented by^FourIs linear having 1 to 18 carbon atoms
Or a group that becomes a branched alkylene group;^Five, R⁶Is
Represents a linear or branched alkylene group having 1 to 18 carbon atoms
You. Q is the following general formula (4a) or (4b)

Embedded image Wherein R ⁸ and R ⁹ are a hydrogen atom or a carbon atom
And represents a linear, branched or cyclic alkyl group of 1 to 8. Alternatively, R ⁸ and R ⁹ may form a ring, and when forming a ring, R ⁸ and R ^{9 each} represent a linear or branched alkylene group having 1 to 8 carbon atoms. R ^8a represents a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 7 carbon atoms, and R ^8a -C
The H and R ⁹ may form a ring, when they form a ring, R ^8a -CH is R ⁸ is a carbon number 1 represented by R ^8a -CH ₂
And R ⁹ represents a linear or branched alkylene group having 1 to 8 carbon atoms. R ¹³ is a linear or branched alkylene group having 1 to 10 carbon atoms, and d is 0 or an integer of 1 to 10. A
Represents a c-valent aliphatic or alicyclic saturated hydrocarbon group having 1 to 50 carbon atoms, an aromatic hydrocarbon group or a heterocyclic group,
In these groups, a hetero atom may be interposed, and a part of the hydrogen atom bonded to the carbon atom may be substituted by a hydroxyl group, a carboxyl group, a carbonyl group or a fluorine atom. B is -CO-O-, -NHCO-O-
Or -NHCONH-. c is 2-8, c 'is 1
It is an integer of 7. m is 0 or a positive integer, n is a positive integer, and m + n = y. p1 and p2 are positive numbers, q11 and q
12 is a positive number, and 0 <p1 / (p1 + q11 + q12
+ P2) ≦ 0.8, 0 <q11 / (p1 + q11 + q1)
2 + p2) ≦ 0.8, 0 <q12 / (p1 + q11 + q
12 + p2) ≦ 0.8, p1 + q11 + q12 + p2 =
It is a number that satisfies 1. Claim 2: (A): an organic solvent (B): a polymer compound having one or more acid labile groups as a base resin is further provided with a C—O—C group within and / or between molecules. A polymer compound having a weight average molecular weight of 1,000 to 500,000 cross-linked by a cross-linking group having the formula (C): an acid generator, wherein the base resin is represented by the following general formula (1 ′) A polymer compound having a repeating unit represented by the formula and having a weight average molecular weight of 1,000 to 500,000 is added to a halogenated alkyl ether compound represented by the following general formula (VI) or (VII); 5
a chemically amplified positive resist characterized by being a polymer compound represented by the following general formula (3a'-1) and / or (3a'-2) obtained by reacting the compound represented by b): material.

Embedded image

Embedded image (Wherein, 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 A positive integer,
It is a number that satisfies x + y ≦ 5. R ⁴ and R ^{5 each} represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, and R ⁶ represents a monovalent group which may have a heteroatom having 1 to 18 carbon atoms. R ⁴ and R ⁵ , R ⁴ and R ⁶ , R ⁵ and R ⁶ may form a ring, and when forming a ring, R ⁴ , R ⁵ and R ⁶ each represent a hydrocarbon group; It represents a linear or branched alkylene group having 1 to 18 carbon atoms. Z represents a halogen atom. Q is the following general formula (4a) or (4b)

Embedded image Wherein R ⁸ and R ⁹ are a hydrogen atom or a carbon atom
And represents a linear, branched or cyclic alkyl group of 1 to 8. Alternatively, R ⁸ and R ⁹ may form a ring, and when forming a ring, R ⁸ and R ^{9 each} represent a linear or branched alkylene group having 1 to 8 carbon atoms. R ¹³ is a linear or branched alkylene group having 1 to 10 carbon atoms, and d is 0 or an integer of 1 to 10. A represents a c-valent aliphatic or alicyclic saturated hydrocarbon group having 1 to 50 carbon atoms, an aromatic hydrocarbon group or a heterocyclic group, and these groups may have a hetero atom interposed;
Some of the hydrogen atoms bonded to the carbon atoms are hydroxyl groups,
It may be substituted by a carboxyl group, a carbonyl group or a fluorine atom. B is -CO-O-, -NHCO
-O- or -NHCONH- is shown. c is 2 to 8, c '
Is an integer of 1 to 7. m is 0 or a positive integer, n is a positive integer, and m + n = y. p1 and p2 are positive numbers, q1
1, q12 are positive numbers, and 0 <p1 / (p1 + q11 +
q12 + p2) ≦ 0.8, 0 <q11 / (p1 + q11)
+ Q12 + p2) ≦ 0.8, 0 <q12 / (p1 + q1)
1 + q12 + p2) ≦ 0.8, p1 + q11 + q12 +
This is a number that satisfies p2 = 1. (3) Claim 3: An acid labile group represented by the following general formula (6) as a base resin, wherein a phenolic hydroxyl group of the polymer compound represented by the formula (3a'-1) and / or (3a'-2) is 2. A polymer compound having q2 moles of a tert-alkyl group, trialkyl group or ketoalkyl group introduced therein.
Or the resist material according to 2.

Embedded image (In the formula, R ⁷ represents a tertiary alkyl group having 4 to 12 carbon atoms. A is an integer of 0 to 6.) Claim 4: Formulas (3a′-1) and / or
Or a compound represented by the following general formula (3b'-1) or (3b'-2) in which an acid labile group represented by the above formula (6) is introduced into a phenolic hydroxyl group of a polymer compound represented by (3a'-2). 4. A resist material according to claim 3, wherein the polymer compound is used.

Embedded image (Wherein, R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ , R ⁷ , Q, x, y,
m, n, a, p1, p2, q11, and q12 have the same meaning as described above. Claim 5: (A): an organic solvent (B): a polymer compound having one or more acid labile groups as a base resin further has a C—O—C group within and / or between molecules. A polymer compound having a weight average molecular weight of 1,000 to 500,000 cross-linked by a cross-linking group having the following formula (C): an acid generator; A polymer compound having a repeating unit represented by the formula and having a weight average molecular weight of 1,000 to 500,000 is added to an alkenyl ether compound represented by the following general formula (I) or (II) or the following general formula (VI) or The following general formula (3c ′) obtained by reacting a halogenated alkyl ether compound represented by (VII)
A chemically amplified positive resist material characterized by being a polymer compound represented by -1) and / or (3c'-2).

Embedded image

Embedded image (Wherein, 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 A positive integer,
It is a number that satisfies x + y ≦ 5. Q is the following general formula (4
a) or (4b)

Embedded image Wherein R ⁸ and R ⁹ are a hydrogen atom or a carbon atom
And represents a linear, branched or cyclic alkyl group of 1 to 8. Alternatively, R ⁸ and R ⁹ may form a ring, and when forming a ring, R ⁸ and R ^{9 each} represent a linear or branched alkylene group having 1 to 8 carbon atoms. R ^8a represents a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 7 carbon atoms, and R ^8a -C
The H and R ⁹ may form a ring, when they form a ring, R ^8a -CH is R ⁸ is a carbon number 1 represented by R ^8a -CH ₂
And R ⁹ represents a linear or branched alkylene group having 1 to 8 carbon atoms. R ¹³ is a linear or branched alkylene group having 1 to 10 carbon atoms, and d is 0 or an integer of 1 to 10. A
Represents a c-valent aliphatic or alicyclic saturated hydrocarbon group having 1 to 50 carbon atoms, an aromatic hydrocarbon group or a heterocyclic group,
In these groups, a hetero atom may be interposed, and a part of the hydrogen atom bonded to the carbon atom may be substituted by a hydroxyl group, a carboxyl group, a carbonyl group or a fluorine atom. B is -CO-O-, -NHCO-O-
Or -NHCONH-. c is 2-8, c 'is 1
It is an integer of 7. m is 0 or a positive integer, n is a positive integer, and m + n = y. p1 and p2 are positive numbers, q11 and q
12 is a positive number, and 0 <p1 / (p1 + q11 + q12
+ P2) ≦ 0.8, 0 <q11 / (p1 + q11 + q1)
2 + p2) ≦ 0.8, 0 <q12 / (p1 + q11 + q
12 + p2) ≦ 0.8, p1 + q11 + q12 + p2 =
It is a number that satisfies 1. Claim 6: Formula (3a′-1) and / or
Or an acid labile group represented by the following general formula (6) to a phenolic hydroxyl group of the polymer compound represented by (3a'-2):
6. The resist material according to claim 5, wherein a polymer compound having q2 mol of a tert-alkyl group, a trialkyl group or a ketoalkyl group introduced therein is used.

Embedded image (In the formula, R ⁷ represents a tertiary alkyl group having 4 to 12 carbon atoms. A is an integer of 0 to 6.) Claim 7: Formulas (3a′-1) and / or
Or a polymer compound in which q1 mol of an acid labile group represented by the following general formula (5) is introduced into a phenolic hydroxyl group of the polymer compound represented by (3a'-2). Or the resist material according to 6.

Embedded image (Wherein R ⁴ and R ⁵ represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, and R ⁶ may have a heteroatom having 1 to 18 carbon atoms. R ⁴ and R ⁵ , R ⁴ and R ⁶ , R ⁵ and R ⁶ may form a ring, and when forming a ring, R ⁴ and R ⁵ , R ⁶ represents a linear or branched alkylene group having 1 to 18 carbon atoms.) Claim 8: An onium salt and / or a diazomethane derivative is blended as the component (C). 1
8. The resist material according to any one of claims 1 to 7. (9) The resist material according to any one of (1) to (8), wherein a basic compound is blended as the component (D). (10) The resist material according to (9), wherein an aliphatic amine is blended as the component (D). Claim 11: As a component (E), ≡C-COOH is present in the molecule.
The resist material according to claim 1, further comprising an aromatic compound having a group represented by the formula: Claim 12: Further, as a base resin different from the component (F) and the component (B), one or two hydrogen atoms of a phenolic hydroxyl group of a polymer compound having a repeating unit represented by the following general formula (1) are used. 2. A high molecular weight compound having a weight average molecular weight of 3,000 to 300,000 partially substituted with an average of 0 to 80 mol% as a whole by at least one kind of acid labile group. 12. The resist material according to any one of items 1 to 11.

Embedded image (Wherein, 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 A positive integer,
It is a number that satisfies x + y ≦ 5. Claim 13: The component (F) has a weight average molecular weight of 3,0 having a repeating unit represented by the following general formula (10).
13. The resist material according to claim 12, wherein a polymer compound of from 00 to 300,000 is blended.

Embedded image(Where R¹, R^Two, R^Four, R^Five, R⁶Is the same as above
And R¹⁴Is -CR^FourR ^FiveOR⁶Acid labile groups different from
Where e and f are 0 or positive numbers, g is a positive number, and e + f + g
= 1, 0 ≦ e / (e + f + g) ≦ 0.5, 0.4
≦ g / (e + f + g) ≦ 0.9. Claim 14: In addition, (G): a dissolution controlling agent is compounded.
The laser according to any one of claims 1 to 13, characterized in that:
Zyst material. Claim 15: The composition further contains (H): an ultraviolet absorber.
The method according to any one of claims 1 to 14, wherein
Resist material. Claim 16: In addition, (I): acetylene alcohol derivative
The body according to any one of claims 1 to 15, wherein the body is blended.
2. The resist material according to claim 1. Claim 17: (i) The chemical booster according to any one of claims 1 to 16
Applying a width-positive resist material onto the substrate;
i) Next, after the heat treatment, a wavelength of 30
Exposure with high energy beam or electron beam below 0nm
Step and (iii) heat treatment if necessary, and then development
And developing using a liquid.
The method of forming the blade.

Here, when the polymer compound as described above is blended in a resist material as a base resin, the polymer compound is cross-linked by a cross-linking group having a C—O—C group. And the dissolution contrast after exposure is large.

That is, in the case of a polymer in which an alkoxyalkyl group is independently added to the side chain, the elimination reaction proceeds with a weak acid, so that it is difficult to form a T-top shape. Therefore, there is a disadvantage that the pattern shape becomes extremely thin with the lapse of time from exposure to heat treatment. In addition, since the dissolution inhibiting effect on alkali is low, a high substitution rate compound must be used in order to obtain a dissolution contrast, which has the disadvantage 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 tert-butoxycarbonyl group, when this is blended with a resist material, the alkali dissolution inhibiting property is improved, and there is an advantage that a dissolution contrast can be obtained at a low substitution rate or heat resistance is good. However, an acid generator that generates a strong acid such as trifluoromethanesulfonic acid is required in order to be desorbed and made alkali-soluble, and when such an acid is used, the T-top shape is easily formed as described above. This has the disadvantage that

For such a polymer, as described above, C and C may be used within a molecule and / or between molecules as obtained by reacting a part of a 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 -OC group has a disadvantage that a polymer in which a side chain is protected by an acetal group has low heat resistance.
T- in a polymer protected with a butoxycarbonyl group
This eliminates the disadvantage that the top shape is easily formed.

On the other hand, as an effect of the polymer compound used for the chemically amplified positive resist composition of the present invention, the polymer compound of the present invention is crosslinked by a crosslinking group having an acid-labile C—O—C group. , Because it is protected by acid labile groups, the weight average molecular weight in the unexposed portion of the resist film and the solubility in an alkali developing solution do not change, but the weight average molecular weight in the exposed portion of the resist film has occurred. After decomposition by acid, the weight-average molecular weight of the alkali-soluble base resin before being protected by cross-linking and acid-labile groups with the elimination of acid-labile groups is returned. Since the dissolution contrast is greatly increased, the resolution can be increased as a result.

When a crosslinking group having a C—O—C group is decomposed by an acid, an alcohol compound (diol, triol, polyol compound, etc.) is produced. The affinity is improved, and as a result, higher resolution can be achieved.

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

That is, a chemically amplified positive resist material using the above-mentioned polymer compound as a base resin has much less problems than conventional ones, such as a tendency to have a T-top shape, a narrow pattern shape, and lack of heat resistance. 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 by the composition. It becomes a chemically amplified positive resist material having excellent adaptability and reproducibility.

Hereinafter, the present invention will be described in more detail. 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. Intra- and / or intermolecular C-
It is a polymer compound having a weight average molecular weight of 1,000 to 500,000 crosslinked by a crosslinking group having an OC group.

In the above polymer compound, a part of the phenolic hydroxyl groups of the polymer compound having a repeating unit represented by the following general formula (1) is partially substituted with an acid labile group, and the remaining phenolic hydroxyl group is A polymer compound which is cross-linked by a cross-linking group having a C—O—C group between and / or between molecules obtained by reacting a part of a hydroxyl group with an alkenyl ether compound or a halogenated alkyl ether compound. it can.

[0021]

Embedded image

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, preferably 1 to 5, more preferably 1 to 3 carbon atoms. Shows, as 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 a cyclohexyl group and a cyclopentyl group.
X is 0 or a positive integer, y is a positive integer, and x +
It satisfies y ≦ 5, but y is 1 to 3, especially 1 to
It is preferably 2.

Specifically, the polymer compound according to the present invention is characterized in that the polymer compound having a repeating unit represented by the following general formula (2) has a portion of a phenolic hydroxyl group represented by R and an alkenyl ether compound or a halogenated compound. It can be a polymer compound cross-linked by a cross-linking group having a C—O—C group in a molecule and / or between molecules obtained by a reaction with an alkyl ether compound.

[0024]

Embedded image (Wherein, 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, and is 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 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, the 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 1-2 and m is 0-1.

As the acid labile group to be substituted for the hydrogen atom of the phenolic hydroxyl group or the acid labile group of R ³ , various groups are selected, and particularly, 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]

Embedded image

In the formula, R ⁴ and R ⁵ represent a hydrogen atom or a group having 1 to 1 carbon atoms.
8, preferably 1 to 6, more preferably 1 to 5, a linear, branched or cyclic alkyl group, and R ⁶ has 1 to 18 carbon atoms, preferably 1 to 10, more preferably 1 to 8 carbon atoms.
A monovalent hydrocarbon group which may have a hetero atom such as an oxygen atom, wherein 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
⁶ represents a linear or branched alkylene group having 1 to 18, preferably 1 to 10, and more preferably 1 to 8 carbon atoms. R ⁷ is 4 to 12 carbon atoms, preferably 4 to 8, more preferably shows a tertiary alkyl group of 4 to 6. Also, a
Is an integer of 0 to 6.

R^Four, R^FiveLinear or branched having 1 to 8 carbon atoms
Or, as a cyclic alkyl group, R ^TwoWith what was explained in
Similar groups are mentioned.

R ⁶ represents a linear, branched or cyclic alkyl group, a phenyl group, a p-methylphenyl group,
Unsubstituted or substituted aryl groups such as alkoxy-substituted phenyl groups such as ethylphenyl group and p-methoxyphenyl group; aralkyl groups such as benzyl group and phenethyl group; and those groups having an oxygen atom or bonded to a carbon atom Examples of such groups include an alkyl group represented by the following formula, in which a hydrogen atom is substituted by a hydroxyl group, or two hydrogen atoms are substituted by an oxygen atom to form a carbonyl group.

[0031]

Embedded image

R ⁷ is tert-butyl, 1-methylcyclohexyl, 2- (2-methyl)
An adamantyl group and a tert-amyl group can be exemplified.

As the acid labile group represented by the above formula (5), specifically, for example, 1-methoxyethyl group, 1-ethoxyethyl group, 1-n-propoxyethyl group, 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 group such as 1-ethoxy-1-methyl-ethyl group, tetrahydrofuranyl group, cyclic acetal group such as tetrahydropyranyl group and the like, preferably ethoxyethyl group, Butoxyethyl group 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
rt-amyloxycarbonylmethyl group and the like.
Further, as the tert-alkyl group, tert-
Examples thereof include a butyl group, a tert-amyl group, a 1-methylcyclohexyl group and the like. 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]

Embedded image

The crosslinking group having a C—O—C group includes a group represented by the following general formula (4a) or (4b).

[0036]

Embedded image (Wherein 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 a ring is formed, 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,
In these groups, a hetero atom may be interposed, and a part of the hydrogen atom bonded to the carbon atom may be substituted by a hydroxyl group, a carboxyl group, a carbonyl group or a fluorine atom. B is -CO-O-, -NHCO-O-
Or -NHCONH-. c is 2-8, c 'is 1
It is an integer of 7. )

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

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

[0039]

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As a specific example of the polymer compound according to the present invention, a hydrogen atom of a phenolic hydroxyl group represented by R of a polymer compound having a repeating unit represented by the following general formula (3) is obtained. An oxygen atom is represented by the above general formula (4)
Examples of the polymer include a polymer compound crosslinked intra- and / or intermolecularly by a crosslinking group having a C—O—C group represented by a) or (4b).

[0041]

Embedded image(Wherein R is a hydroxyl group or OR^ThreeAt least one
The individual is a hydroxyl group. R¹Represents a hydrogen atom or a methyl group
Then R^TwoIs a linear, branched or cyclic C 1-8
Represents a alkyl group. R^ThreeRepresents an acid labile group. R^Four, R^FiveIs
A hydrogen atom or a linear, branched or cyclic C1-C8
Represents an alkyl group;⁶Is a heteroatom having 1 to 18 carbon atoms
A monovalent hydrocarbon group optionally having^FourWhen
R^Five, R^FourAnd R⁶, R ^FiveAnd R⁶And may form a ring, a ring
When forming R^Four, R^Five, R⁶Each have 1 carbon atom
To 18 linear or branched alkylene groups. R⁷
Represents a tertiary alkyl group having 4 to 12 carbon atoms. p1, p2
Is a positive number, q1 and q2 are 0 or a positive number, and 0 <p1 /
(P1 + q1 + q2 + p2) ≦ 0.8, 0 ≦ q1 / (p
1 + q1 + q2 + p2) ≦ 0.8, 0 ≦ q2 / (p1 +
q1 + q2 + p2) ≦ 0.8, p1 + q1 + q2 + p2
= 1, but q1 and q2 become 0 at the same time.
Never. a is 0 or a positive integer of 1 to 6.
x, y, k, m, and n have the same meanings as above.
You. Note that p1 + p2 = p and q1 + q2 = q. )

Here, R, R ^{1 to} R ⁷ , x, y, k, m,
Specific examples and preferred ranges of n and a are as described above. Also,
p1 and p2 are positive numbers, q1 and q2 are 0 or positive numbers, and 0
<P1 / (p1 + q1 + q2 + p2) ≦ 0.8, 0 ≦ q
1 / (p1 + q1 + q2 + p2) ≦ 0.8, 0 ≦ q2 /
(P1 + q1 + q2 + p2) ≦ 0.8, p1 + q1 + q
Although the number satisfies 2 + p2 = 1, q1 and q2 do not become 0 at the same time.

More preferably, p1, p2, q1, q2
Are as follows.

[0044]

(Equation 1) Further, it is desirable that q1 / (q1 + q2) is 0 to 1, more preferably 0.5 to 1, and still more preferably 0.7 to 1.

Examples of the polymer compound include compounds represented by the following formulas (3′-1) and (3′-2).

[0046]

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[0047]

Embedded image Formula (3'-1) shows a state of intermolecular bond, and Formula (3'-2) shows a state of intramolecular bond, and these may be used alone or in combination.

Wherein Q is a crosslinking group having a C—O—C group,
Typically, the crosslinking group represented by the above formula (4a) or (4b), particularly the formula (4a ′), (4b ′), (4a ″), (4
b "). In this case, the crosslinking group is 3
In the case where the valence is equal to or more than 3 in the above formula (3),
More than Q are combined.

[0049]

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In the polymer compound of the present invention, a part of the hydrogen atom of the phenolic hydroxyl group has an acid labile group and the above-mentioned C—O
Which is substituted with a crosslinking group having a -C group,
More preferably, the total of the acid labile group and the cross-linking group is more than 0 mol% on average and 80 mol% or less, especially 2 to 50 mol%, based on all hydrogen atoms of the phenolic hydroxyl group of the compound of the formula (1). Preferably, there is.

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

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

The dimensions 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 ranges. In the polymer compound of the present invention, the content of a crosslinking group having a C—O—C group and an acid labile group affects the dissolution rate contrast of a resist film,
This is related to characteristics of the resist material such as pattern dimension control and pattern shape.

Each of the polymer compounds according to the present invention has a weight average molecular weight (measurement method is described later) of 1,0.
00 to 500,000, preferably 3,000 to 30,
000. Weight average molecular weight of 1,000
If less than, the resist material will be inferior in heat resistance,
If it exceeds 500,000, the alkali solubility decreases and the resolution deteriorates.

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

As a method for producing a polymer compound according to the present invention, for example, a phenolic hydroxyl group of a polymer compound having a repeating unit represented by the general formula (1) is added to an acid labile group represented by the general formula (5). And then isolated, and reacted with an alkenyl ether compound or a halogenated alkyl ether compound to give C- within the molecule and / or between the molecules.
A method of crosslinking with a crosslinking group having an OC group, or a method of crosslinking with an alkenyl ether compound or a halogenated alkyl ether compound to cause crosslinking within a molecule and / or between molecules with a group represented by C—O—C and isolation. Thereafter, a method of introducing an acid labile group represented by the general formula (5) or a 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) are collectively performed. Examples of the method include a method in which 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 performed at once. In addition, the polymer compound obtained as described above 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 a first method, the formula (1 ′)
A method using a polymer compound having a repeating unit represented by the following, an alkenyl ether compound represented by the following general formula (I) or (II), and a compound represented by the following general formula (5a). A polymer compound having a repeating unit represented by (1 ′), and a compound represented by the following general formula (VI):
Alternatively, a method using a halogenated alkyl ether compound represented by the formula (VII) and a compound represented by the following general formula (5b) is exemplified.

[0058]

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Here, R ¹ , R ² , R ⁹ , x, y and p
1, p2 has the same meaning as described above. q11 and q12 have the same meanings as q1 and q2, respectively, but never become zero. p1 + p2 + q11 + q12 = 1. R ⁵ and R ⁶ have the same meaning as described above, and R ^4a and R ^8a
Represents a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 7 carbon atoms. Further, R ^4a —CH and R ⁵ or R ^4a
The -CH and R ⁶ may form a ring, when they form a ring, R ^4a -CH is R ⁴ is a straight-chain or branched having 1 to 18 carbon atoms represented by R ^4a -CH ₂ R ⁵ and R ^{6 each} represent a linear or branched alkylene group having 1 to 18 carbon atoms. R ^8a —CH and R ⁹ may form a ring, and when forming a ring, R ^8a —CH is R ^8a
R ⁸ represented by -CH ₂ represents a group comprising a linear or branched alkylene group having 1 to 8 carbon atoms, R ⁹ is 1 to 8 carbon atoms
Represents a linear or branched alkylene group.

Further, in the alkenyl ether compound represented by the formula (I) or (II), A has a c value (c is 2 to
6 is an organic group wherein B is -CO-O-, -NH
Shows the CO-O- or -NHCONH-, R ¹³ is a straight or branched alkylene of 1 to 10 carbon atoms, d
Represents an integer of 0 or 1 to 10, and c represents an integer of 2 to 8.

The c-valent organic group of A is, specifically, a hydrocarbon group preferably having 1 to 50 carbon atoms, particularly 1 to 40 carbon atoms such as O, NH, N (CH ₃ ), S and SO ₂ . An unsubstituted or hydroxyl group, a carboxyl group, a carbonyl group or a fluorine atom-substituted alkylene group which may have a hetero atom interposed, preferably an arylene group having 6 to 50 carbon atoms, particularly 6 to 40 carbon atoms, and these alkylene groups and arylene groups are A bonded group, a group having a c "valence (c" is an integer of 3 to 8) from which a hydrogen atom bonded to a carbon atom of each of the above groups has been eliminated, and a c-valent heterocyclic group; And the above-mentioned hydrocarbon groups are bonded.

Specifically, the following can be mentioned as A.

[0063]

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[0064]

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[0065]

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[0066]

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

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

[0069]

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[0070]

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[0071]

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[0072]

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[0073]

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

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

[0076]

Embedded image (R ^8a , R ⁹ and R ¹³ have the same meaning as described above.)

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

[0078]

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[0079]

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

[0081]

Embedded image(Where m + n = y, m, n, x, y, p1, p
2, q11, q12, R ¹, R^Two, R^Four, R^Five, R⁶, Q is
Each has the same meaning as above. )

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

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

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

When the above reactions are carried out collectively without isolation,
The order 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 first, the compound represented by the general formula (5a) is added, After the reaction has sufficiently proceeded, it is preferable to add the alkenyl ether compound represented by the general formula (I) or (II). For example, the alkenyl ether compound represented by the general formula (I) or (II) and the compound represented by the general formula (5a) are added simultaneously, or the alkenyl ether compound represented by the general formula (I) or (II) is added first. When added, the compound represented by the general formula (I) or (II)
In some cases, some of the reaction points of the alkenyl ether compound represented by are hydrolyzed by the water in the reaction system, and the structure of the resulting polymer compound becomes complicated, making it difficult to control the physical properties.

[0086]

Embedded image (Wherein, R ¹ , R ² , x, y, p1, p2, q11, q1
2, R ⁴ , R ⁵ , R ⁶ and R ⁸ , R ⁹ , R ¹³ , A, B, c,
d has the same meaning as above, and Z is a halogen atom (Cl, Br or I). )

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

In the second method, when the weight average molecular weight is 1,0
And a hydrogen atom of a phenolic hydroxyl group of a polymer compound having a repeating unit represented by the general formula (1 ′) having a molecular weight distribution of 1.0 to 1.5, By reacting p1 mol of the halogenated alkyl ether compound represented by the general formula (VI) or (VII) and q1 mol of the compound represented by the general formula (5b) per mol, for example, the compound represented by the above formula (3a′-1) ),
A 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,
Aprotic polar solvents such as tetrahydrofuran and dimethylsulfoxide are preferred, and they may be used alone or as a mixture of two or more.

The base is preferably triethylamine, pyridine, diisopropylamine, potassium carbonate, or the like. The amount of the base used is (p1) per mole of the phenolic hydroxyl group of the polymer compound represented by the general formula (1).
+ Q1) It is preferably at least mol.

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

As described above, the polymer represented by the formula (5a) or (5b) is reacted with the polymer compound having the repeating unit represented by the formula (1 ') to give a compound represented by the following formula (7). After obtaining it, it is isolated and then of the formula (I)
Crosslinking may be performed using a compound represented by (II) or (VI) or (VII).

[0094]

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

[0096]

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The method for introducing the acid labile group of the above formula (6) is as follows.
It is preferable to carry out the reaction in a solvent in the presence of a base.

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

As the base, triethylamine, pyridine, imidazole, diisopropylamine, potassium carbonate and the like are preferable. Preferably it is molar.

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

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

The polymer compound represented by the general formula (3a'-1) or (3a'-2) obtained by the first or second method may be added to the original compound represented by the general formula (1 The tert-alkylation or ketoalkylation can be performed by reacting q2 mol of a tert-alkylating agent and a ketoalkyl compound with respect to 1 mol of the phenolic hydroxyl group of the polymer compound represented by ').

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

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

As the acid for the catalyst, hydrochloric acid, sulfuric acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, pyridinium p-toluenesulfonate and the like are preferably used. ) Is preferably 0.1 to 10 mol% based on 1 mol of the phenolic hydroxyl group of the polymer compound represented by the formula (1).

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

As the tert-alkylating agent, iso-
Butene, 2-methyl-1-butene, 2-methyl-2-butene, and the like. Examples of the ketoalkyl compound include α-angelicalactone, 2-cyclohexen-1-one,
5,6-dihydro-2H-pyran-2-one and the like.

The general formulas (3a'-1) and (3a'-
The polymer compound having the repeating unit represented by the following general formula (3c′-1) or (3c′-2) directly without passing through the polymer compound represented by 2) is added to the acid represented by the general formula (6). 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 as necessary.

[0109]

Embedded image (Wherein, R ¹ , R ² , Q, p1, p2, q11, q12,
x and y each have the same meaning as described 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 an acid labile group is introduced as described above with respect to 1 mol of all hydroxyl groups of the polymer compound of the formula (1 ′), and then a different acid labile group is introduced in the same manner as described above. By introducing q2 moles of the above, it is possible to obtain a polymer compound in which two or more such acid labile groups are introduced or the above operation is repeated as appropriate.

The chemically amplified positive resist composition of the present invention comprises:
The polymer compound is used as a base polymer and contains the following components. (A): an organic solvent; (B): a polymer compound obtained by the above method as a base resin; (C): an acid generator; (D): a basic compound; and (E): in the molecule. An aromatic compound having a group represented by C-COOH.

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

[0113]

[Of 60] (Wherein, 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 A positive integer,
It is a number that satisfies x + y ≦ 5. (G): dissolution controlling 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 which can dissolve the acid generator, the base resin, the dissolution controlling agent and the like. Examples of such an organic solvent include ketones such as cyclohexanone, methyl-2-n-amyl ketone, 3-methoxybutanol, 3-methyl-3-methoxybutanol,
Alcohols such as -methoxy-2-propanol and 1-ethoxy-2-propanol, and ethers such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether and diethylene glycol dimethyl ether , Propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl-3-methoxypropionate, ethyl-3-ethoxypropionate, tert-acetate
Esters such as t-butyl, tert-butyl propionate, and propylene glycol mono-tert-butyl ether acetate can be used. One of these can be used alone, or two or more can be used as a mixture, but are not limited thereto. It is not something to be done. In the present invention, among these organic solvents, diethylene glycol dimethyl ether and 1-
In addition to ethoxy-2-propanol and ethyl lactate, propylene glycol monomethyl ether acetate as a safe solvent and a mixed solvent thereof are preferably used.

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

Examples of the acid generator (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, trifluoromethanesulfonate Onium salts such as dicyclohexylphenylsulfonium and dicyclohexylphenylsulfonium p-toluenesulfonate; 2-cyclohexylcarbonyl-2- (p-toluenesulfonyl) propane;
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 and bis (tert-butylsulfonyl) diazomethane; disulfones such as diphenyldisulfone and dicyclohexyldisulfone Derivatives, nitrobenzylsulfonate derivatives such as 2,6-dinitrobenzyl p-toluenesulfonate and 2,4-dinitrobenzyl p-toluenesulfonate, 1,2,3-tris (methanesulfonyloxy) benzene, 3-tris (trifluoromethanesulfonyloxy) benzene,
1,2,3-tris (p-toluenesulfonyloxy)
Sulfonate derivatives such as benzene, phthalimido-yl-triflate, phthalimido-yl-tosylate, 5-norbornene-2,3-dicarboximide-
Imido-yl-sulfonate derivatives such as yl-triflate, 5-norbornene-2,3-dicarboximido-yl-tosylate, and 5-norbornene-2,3-dicarboximido-yl-n-butylsulfonate; But triphenylsulfonium trifluoromethanesulfonate, trifluoromethanesulfonate (p-
tert-butoxyphenyl) diphenylsulfonium, tris trifluoromethanesulfonate (p-ter
(t-butoxyphenyl) sulfonium, triphenylsulfonium p-toluenesulfonate, p-toluenesulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, tris (pt)
onium salts such as tert-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 effect of improving the rectangularity, and the diazomethane derivative is excellent in the effect of reducing the standing wave. However, by combining the two, fine adjustment of the profile can be performed.

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

As the base resin other than the crosslinked polymer compound of the component (B) of the component (F), particularly, the weight average molecular weight having a repeating unit represented by the following general formula (10) is 3 2,000 to 300,000 high molecular compounds are preferably used.

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

[0120]

Embedded image

In the above formula, R ¹ , R ² , R ⁴ , R ⁵ , R
⁶ has the same meaning as described above, and 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.

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

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

Further, even in the base resin of the component (F), when the molecular weight distribution (Mw / Mn) is wide, a low molecular weight or high molecular weight polymer is present, and when a large amount of low molecular weight polymer is present, heat resistance is low. In some cases, when a high-molecular-weight polymer is present in a large amount, it may be difficult to dissolve in alkali, and may cause tailing after pattern formation. Therefore, as the pattern rule becomes finer, the influence of such molecular weight and molecular weight distribution tends to increase. Therefore, in order to obtain a resist material suitably used for fine pattern dimensions, the molecular weight distribution of the base resin must be as follows. 0
It is preferably a narrow dispersion of 2.5 to 2.5, particularly 1.0 to 1.5.

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

In the resist composition of the present invention, a dissolution controlling agent can be further added as a component (G), whereby the contrast can be improved. As the dissolution controlling agent, the hydrogen atom of the phenolic hydroxyl group of a compound having an average molecular weight of 100 to 1,000, preferably 150 to 800, and having two or more phenolic hydroxyl groups in the molecule is entirely formed by an acid labile group. And a compound substituted at an average ratio of 0 to 100%.

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

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

[0129]

Embedded image

[0130]

Embedded image

[0131]

Embedded image (Where R ⁵¹ and R ⁵² are each a hydrogen atom or a linear or branched alkyl group or alkenyl group having 1 to 8 carbon atoms, and R ⁵³ is a hydrogen atom or a linear chain having 1 to 8 carbon atoms. Or branched alkyl or alkenyl group, or-
(R ⁵⁷ ) _h —COOH, and R ⁵⁴ is — (CH ₂ ) _i —
(I = 2 to 10), an arylene group having 6 to 10 carbon atoms, a carbonyl group, a sulfonyl group, an oxygen atom or a sulfur atom, R
⁵⁵ is an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, a carbonyl group, a sulfonyl group, an oxygen atom or a sulfur atom, and ^R56 is a hydrogen atom or a linear or branched chain having 1 to 8 carbon atoms. An alkyl group, an alkenyl group, a phenyl group or a naphthyl group each substituted with a hydroxyl group,
⁵⁷ is a linear or branched alkylene group having 1 to 10 carbon atoms. J is an integer of 0 to 5, and 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. Such a number. α is the equation (viii), (ix)
Is a number with a molecular weight of 100 to 1,000. )

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

Here, the acid labile group of the dissolution controlling agent includes the groups represented by the above formulas (5) and (6), t
tert-alkyl groups, trialkylsilyl groups, β-ketoalkyl groups and the like.

The compound (dissolution controller) in which the phenolic hydroxyl group is partially substituted with an acid labile group is 0 to 50 parts, preferably 5 to 50 parts, per 100 parts of the base resin.
Parts, more preferably 10 to 30 parts, and they can be used alone or in combination of two or more. If the amount is less than 5 parts, the resolution may not be improved. If the amount is more than 50 parts, the pattern may be reduced in film thickness and the resolution may be reduced.

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

The resist composition of the present invention may have a weight average molecular weight of more than 1,000 and not more than 3,000 as another dissolution controlling agent instead of or in addition to the above dissolution controlling agent, and a phenolic hydroxyl group in the molecule. And a compound in which the hydrogen atom of the phenolic hydroxyl group is partially substituted by an acid labile group at an average rate of 0% or more and 60% or less as a whole.

In this case, as the compound in which the hydrogen atom of the phenolic hydroxyl group is partially substituted with such an acid labile group,
One or more compounds selected from compounds having a repeating unit represented by the following general formula (11) and having a weight average molecular weight of more than 1,000 and not more than 3,000 are preferred.

[0138]

Embedded image (Where 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 controlling agent includes a group represented by the general formula (5), a group represented by the general formula (6), a tert-alkyl group, a trialkylsilyl group, And a ketoalkyl group.

The compounding amount of the above-mentioned another dissolution controlling agent is based on the total dissolution controlling agent and the dissolution controlling agent as a whole.
0 to 50 parts, especially 0 to 30 parts, preferably 1 to 0 parts
It is preferable that the amount be in the range of not less than parts.

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

As the basic compound as the component (D), a compound capable of suppressing the rate of diffusion of the acid generated from the acid generator into the resist film is suitable. By the compounding, the diffusion rate of the acid in the resist film is suppressed, the resolution is improved, the sensitivity change after exposure is suppressed, the dependency on the substrate and the environment is reduced, and the exposure margin and the pattern profile are improved. be able to.

Examples of such a basic compound include the following:
Primary, secondary, tertiary aliphatic amines, mixed amines,
Aromatic amines, heterocyclic amines, nitrogen-containing compounds having a carboxy group, nitrogen-containing compounds having a sulfonyl group,
Examples of the compound 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, examples of primary aliphatic amines include 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, and the like.Examples of the secondary aliphatic amines include: 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. Examples of the tertiary aliphatic amines include trimethylamine, triethylamine, tri-n-propylamine, tri-iso-propylamine, and triethylamine. -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'-tetramethyltetraethylenepentamine and the like are exemplified.

Examples of the mixed amines include dimethylethylamine, methylethylpropylamine, benzylamine, phenethylamine and benzyldimethylamine. 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 (for example, pyrrole, 2H-pyrrole, 1-methyl Pyrrole, 2,4-dimethylpyrrole, 2,5-dimethylpyrrole, N-methylpyrrole, etc.), oxazole derivatives (eg, oxazole, isoxazole, etc.), thiazole derivatives (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
-Pyrrolidine), pyrrolidine derivatives (e.g., pyrrolidine, N-methylpyrrolidine, pyrrolidinone, N-methylpyrrolidone, etc.), imidazoline derivatives, imidazolidine derivatives, pyridine derivatives (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 derivatives, pyrimidine derivatives, pyrazine derivatives, pyrazoline derivatives, pyrazolidine derivatives, piperidine derivatives,
Piperazine derivatives, morpholine derivatives, indole derivatives, isoindole derivatives, 1H-indazole derivatives, indoline derivatives, quinoline derivatives (eg, quinoline, 3-quinolinecarbonitrile, etc.), isoquinoline derivatives, cinnoline derivatives, quinazoline derivatives, quinoxaline derivatives, phthalazine derivatives, Purine derivatives, pteridine derivatives, carbazole derivatives, phenanthridine derivatives, acridine derivatives, phenazine derivatives, 1,10
-Phenanthroline derivatives, adenine derivatives, adenosine derivatives, guanine derivatives, guanosine derivatives, uracil derivatives, uridine derivatives and the like.

Further, examples of the nitrogen-containing compound having a carboxy group include aminobenzoic acid, indolecarboxylic acid, and amino acid derivatives (eg, nicotinic acid, alanine, arginine, aspartic acid, glutamic acid, glycine,
Histidine, isoleucine, glycylleucine, leucine, methionine, phenylalanine, threonine, lysine, 3-aminopyrazine-2-carboxylic acid, methoxyalanine), and the like; 3-pyridinesulfonic acid as a nitrogen-containing compound having a sulfonyl group; Pyridinium p-toluenesulfonate and the like are exemplified, and a nitrogen-containing compound having a hydroxy group, a nitrogen-containing compound having a hydroxyphenyl group, and an alcoholic nitrogen-containing compound include 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, piperidineethanol, 1- (2-hydroxyethyl) pyrrolidine, 1- (2-hydroxyethyl) -2-pyrrolidinone, 3-piperidino-1,2-propanediol, 3-
Pyrrolidino-1,2-propanediol, 8-hydroxyurolidine, 3-quinuclidinol, 3-tropanol, 1-methyl-2-pyrrolidineethanol, 1-aziridineethanol, N- (2-hydroxyethyl) phthalimide, N- (2-hydroxyethyl) isonicotinamide and the like are exemplified. Examples of the amide derivative include formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide and the like. Examples of the imide derivative include phthalimide, succinimide, and maleimide. In particular, triethylamine, N, N-dimethylaniline, N-methylpyrrolidone, pyridine, quinoline,
Nicotinic acid, triethanolamine, piperidineethanol, N, N-dimethylacetamide, succinimide and the like are preferred.

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

Further, the aromatic compound having a group represented by ≡C-COOH in the molecule blended as the component (E) in the resist composition of the present invention is, for example, one kind selected from the following groups I and II. Alternatively, two or more compounds can be used, but the present invention is not limited thereto. (E)
By mixing 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] Part or all of the hydrogen atoms of the phenolic hydroxyl group of the compounds represented by the following formulas (12) to (21) is-
R ⁵⁷ —COOH (R ⁵⁷ is a linear or branched alkylene group having 1 to 10 carbon atoms), and a phenolic hydroxyl group C in the molecule and a group D represented by ΔC—COOH The compound whose molar ratio is C / (C + D) = 0.1 to 1.0. [Group II] Compounds represented by the following general formulas (22) and (23).

[0149]

Embedded image

[0150]

Embedded image (Where R ¹ is a hydrogen atom or a methyl group,
R ⁵¹ and R ⁵² each represent a hydrogen atom or a linear or branched alkyl or alkenyl group having 1 to 8 carbon atoms;
⁵³ is a hydrogen atom, a linear or branched alkyl or alkenyl group having 1 to 8 carbon atoms, or — (R ⁵⁷ ) _h —CO
An OR ′ group (R ′ is a hydrogen atom or —R ⁵⁷ —COOH); R ⁵⁴ is — (CH ₂ ) _i — (i = 2 to 10);
-10 arylene groups, carbonyl groups, sulfonyl groups,
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 a carbon atom having 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 is a hydrogen atom or a linear or branched alkyl or alkenyl group, or -R ⁵⁷ -COOH group having 1 to 8 carbon atoms. j is an integer of 0 to 5, and u and h are 0 or 1. s1, t1, s
2, t2, s3, t3, s4, and t4 are respectively 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 which makes the compound of the formula (17) a weight average molecular weight of 1,000 to 5,000, and γ is a number which makes the compound of the formula (18) a weight average molecular weight of 1,000
This is a number from 0 to 10,000. )

[0151]

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

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

[0153]

Embedded image

[0154]

Embedded image

[0155]

Embedded image (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
OOH group. )

[0156]

Embedded image

The aromatic compound having a group represented by ≡C—COOH in the molecule can be used alone or in combination of two or more.

The 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, per 100 parts of the base resin. If the amount is less than 0.1 part, the footing on the nitride film substrate and the effect of improving the PED may not be sufficiently obtained, and if the amount is more than 5 parts, the resolution of the resist material may decrease.

The resist composition of the present invention further comprises (H)
A compound having a molar absorbance 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 reflectivities.

More specifically, pentalene, indene, naphthalene, azulene, peptalene, biphenylene, indacene, fluorene, phenalene, phenanthrene, anthracene, fluoranthene, acephenanthrylene, aceanthrylene, triphenylene, pyrene, chrysene,
Naphthalene, preiaden, picene, perylene, pentaphen, pentacene, benzophenanthrene, anthraquinone, anthrone benzanthrone, 2,7-dimethoxynaphthalene, 2-ethyl-9,10-dimethoxyanthoselan, 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; 2,
3,4-tribitroxybenzophenone, 2,3,4
4′-tetrahydroxybenzophenone, 2,4-dihydroxybenzophenone, 3,5-dihydroxybenzophenone, 4,4′-dihydroxybenzophenone,
Benzophenone derivatives such as 4,4'-bis (dimethylamino) benzophenone; square acid derivatives such as square acid and dimethyl squarate;

[0161]

Embedded image(Where R⁶¹~ R⁶³Are each independently a hydrogen atom, linear
Or a branched alkyl group, a linear or branched
Alkoxy group, linear or branched alkoxyal
A kill group, a linear or branched alkenyl group or an ant
A group. R ⁶⁴Is a substitution optionally containing an oxygen atom
Or an unsubstituted divalent aliphatic hydrocarbon group or an oxygen atom
A substituted or unsubstituted divalent alicyclic carbon which may be contained
Hydrogenated, substituted or unsubstituted, which may contain an oxygen atom
A substituted divalent aromatic hydrocarbon group or an oxygen atom;
⁶⁵Is an acid labile group. J is 0 or 1. E, F,
G is 0 or an integer of 1 to 9 each, and H is a positive number of 1 to 10
It is an integer and satisfies E + F + G + H ≦ 10. )

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

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 or an oxygen atom which may contain 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 a methylene group, an ethylene group, an n-propylene group, an isopropylene group, an n-butylene group and a 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.

The substituted or unsubstituted divalent alicyclic hydrocarbon group which may contain an oxygen atom includes, for example, 1,1
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.

Examples of the substituted or unsubstituted divalent aromatic hydrocarbon group which may contain an oxygen atom include, 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. The term “acid labile group” as used herein means a group obtained by substituting a carboxyl group 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 release a functional group exhibiting alkali solubility. In particular, groups represented by the following general formulas (26a), (26b), and (26c) preferable.

[0168]

Embedded image (Wherein, R ^{66 to} R ⁶⁹ each independently represent a hydrogen atom, a linear or branched alkyl group, a linear or branched alkoxy group, a linear or branched alkoxyalkyl group, Alternatively, it is a branched alkenyl group or an aryl group, and these groups may contain a carbonyl group in the chain, but all of R ^{66 to} R ⁶⁹ must not be hydrogen atoms. ⁶⁶ and R ⁶⁷ may be bonded to each other to form a ring, and R ⁶⁹ is 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 contain a carbonyl group in the chain, and R ⁶⁹ may combine with R ⁶⁶ to form a ring.)

In this case, the above-mentioned linear or branched alkyl group, linear or branched alkoxy group, linear or branched alkoxyalkyl group, linear or branched alkenyl group, aryl group Examples thereof include the same as those described above for R ^{61 to} R ⁶³ .

In the formula (26a), examples of the ring formed by combining R ⁶⁶ and R ⁶⁷ with each other include a cyclohexylidene group, a cyclopentylidene group, a 3-oxocyclohexylidene group, a 3-oxo- Examples thereof include those having 4 to 10 carbon atoms such as a 4-oxacyclohexylidene group and a 4-methylcyclohexylidene group.

In the formula (26b), the ring formed by bonding R ⁶⁶ and R ⁶⁷ to each other includes, for example, 1-silacyclohexylidene group, 1-silacyclopentylidene group, 3-oxo-1- Silacyclopentylidene group, 4-
C3-C3 such as methyl-1-silacyclopentylidene group
9 are mentioned.

In the formula (26c), examples of the ring formed by combining R ⁶⁹ and R ⁶⁶ with each other include a 2-oxacyclohexylidene group, a 2-oxacyclopentylidene group and a 2-oxa-4- Those having 4 to 10 carbon atoms such as a methylcyclohexylidene group are exemplified.

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

Examples of the group represented by the above formula (26b) include trialkylsilyl groups having 3 to 10 carbon atoms such as trimethylsilyl, ethyldimethylsilyl, dimethylpropylsilyl, diethylmethylsilyl, and triethylsilyl. 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, Those having 2 to 8 carbon atoms, such as a dimethoxymethyl group, a diethoxymethyl group, a tetrahydrofuranyl group and a tetrahydropyranyl group, are preferred.

In the above formulas (24) and (25), E, F and G are each 0 or a positive integer of 1 to 9;
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 the compounds represented by the following (27a) to (27j).

[0178]

[Of 75] (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
diarylsulfoxide derivatives such as rt-butoxycarbonyloxyphenyl) sulfoxide, 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]
Diarylsulfone derivatives such as sulfone, benzoquinonediazide, naphthoquinonediazide, anthraquinonediazide, diazo compounds such as diazofluorene, diazotetralone and diazophenanthrone, naphthoquinone-1,2
-Complete or partial ester compound of diazide-5-sulfonic acid chloride and 2,3,4-trihydroxybenzophenone, naphthoquinone-1,2-diazide-4-sulfonic acid chloride and 2,4,4'-trihydroxybenzophenone And quinonediazide group-containing compounds such as complete or partial ester compounds.

Preferred as the ultraviolet absorber are tert-butyl 9-anthracenecarboxylate, tert-amyl 9-anthracenecarboxylate, tert-methoxymethyl 9-anthracenecarboxylate, tert-ethoxyethyl 9-anthracenecarboxylate, Tert-tetrahydropyranyl anthracenecarboxylate, tert-tetrahydrofuranyl 9-anthracenecarboxylate,
A partial ester compound of naphthoquinone-1,2-diazide-5-sulfonic acid chloride and 2,3,4-trihydroxybenzophenone can be exemplified.

The compounding amount of the ultraviolet absorbent (H) is preferably 0 to 10 parts, more preferably 0.5 to 10 parts, and further preferably 1 to 5 parts with respect to 100 parts of the base resin. preferable.

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

As the acetylene alcohol derivative, those represented by the following general formulas (28) and (29) can be suitably used.

[0184]

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

Preferred as acetylene alcohol derivatives are Surfinol 61, Surfinol 82, Surfinol 104, Surfinol 104E, Surfinol 104H, Surfinol 104A, Surfinol TG, Surfinol PC, Surfinol 44
0, Surfynol 465, Surfynol 485 (A
ir Products and Chemicals
Inc. Manufactured). Surfynol (Su
rfynol) is a manufacturer of AirProd in the US
octs and Chemicals Inc. Is a trademark.

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

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

The surfactant is preferably a nonionic surfactant, and examples thereof include perfluoroalkylpolyoxyethylene 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 Chemicals, Inc.)," X-70-
092 "and" X-70-093 "(all manufactured by Shin-Etsu Chemical Co., Ltd.). Preferably, Florad “FC-430” (Sumitomo 3M Limited)
X-70-093 "(Shin-Etsu Chemical Co., Ltd.)
Is mentioned.

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

[0190]

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

[0191]

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

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

[Synthesis Example 2] In a 2 L flask, 100 g of polyhydroxystyrene was added with dimethylformamide 1,100.
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 while stirring at 20 ° C. After reacting for 1 hour, the mixture was neutralized with concentrated aqueous ammonia and the neutralized reaction solution was added dropwise to 10 L of water to obtain a white solid. After filtering this, acetone 5
It was dissolved in 00 ml, dropped into 10 L of water, filtered, and dried in vacuum. From the ¹ H-NMR of the obtained polymer, it was confirmed that the hydrogen atom of the hydroxyl group of polyhydroxystyrene was 27% ethoxyethylated and 3% was crosslinked.

Further, 50 g of the obtained partially crosslinked ethoxyethoxylated polyhydroxystyrene was added to pyridine 5
Of dicarbonate while stirring at 45 ° C.
7 g of tert-butyl were added. After reacting for 1 hour, the reaction solution was added dropwise to 3 L of water to obtain a white solid. After filtration, this was dissolved in 50 ml of acetone, dropped into 2 L of water, filtered, and dried under vacuum to obtain a polymer. The obtained polymer has the following chemical formula (Polym. 2)
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% from ¹ H-NMR.

[Synthesis Example 3] 50 g of polyhydroxystyrene was put into a 2 L flask in 500 ml of dimethylformamide.
, And a catalytic amount of p-toluenesulfonic acid was added.
g, 1,4-di (vinyl ether) cyclohexane 3 g
Was added. After reacting for 1 hour, the mixture was neutralized with concentrated ammonia water, and the neutralized reaction solution was added dropwise to 10 L of water.
A white solid was obtained. After filtering this, acetone 500m
The solution was added dropwise to 10 L of water, filtered, and dried under vacuum. From the ¹ H-NMR of the obtained polymer, it was confirmed that the hydrogen atom of the hydroxyl group of polyhydroxystyrene was ethoxyethylated by 24% and 10% was crosslinked (Po).
lym. 3).

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

[Synthesis Example 8] 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.
While stirring at 0 ° C., ethyl 1-propenyl ether 2
8.2 g was added and reacted for 3 hours. Then, 1,4
3.8 g of butanediol divinyl ether are added,
After reacting for 0.5 hour, the mixture was neutralized with concentrated aqueous ammonia. The reaction solution was solvent-exchanged to ethyl acetate, and purified by liquid separation and purification six times using pure water and a small amount of acetone. Then, the solvent was exchanged for acetone and dropped into 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 chemical formula (Pol
ym. Has a structure represented by 8), ¹ H-NMR hydrogen atoms of the hydroxyl groups of polyhydroxystyrene are 26% ethoxylated propoxylated from, it was confirmed that the 5.5% 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.
While stirring at 0 ° C., ethyl 1-propenyl ether 2
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 solvent-exchanged to ethyl acetate, and purified by liquid separation and purification six times using pure water and a small amount of acetone. Then, the solvent was exchanged for acetone and dropped into 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 obtained partially crosslinked ethoxypropoxylated polyhydroxystyrene was dissolved in 300 g of pyridine, and the mixture was stirred at 40 ° C. with di-dicarbonate.
4.5 g of tert-butyl were 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, dropped into 2 L of water, filtered, and dried in vacuo to obtain a polymer. The obtained polymer was represented by the following chemical formula (Polym.
Having a structure represented by 9), wherein from ¹ H-NMR, the hydrogen atom of the hydroxyl group of polyhydroxystyrene is 21% ethoxypropoxylated, 5% is tert-butoxycarbonylated, and 5.5% is crosslinked. Was confirmed.

Synthesis Example 10 100 g of polyhydroxystyrene and 900 g of tetrahydrofuran were placed in a 2 L flask.
And, after adding 3.9 g of methanesulfonic acid,
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 solvent of this reaction solution was exchanged for ethyl acetate, and the resulting solution was separated and purified six times with pure water. After that, the solvent was exchanged for acetone and dropped into 20 L of pure water to obtain a white solid. This was filtered, washed twice with pure water, filtered, and vacuum dried. The obtained polymer has a structure represented by the following descriptive formula (Polym. 10), and the hydrogen atom of the hydroxyl group of polyhydroxystyrene is 31% ethoxyethylated by ¹ H-NMR, and 5.5% is crosslinked. It was confirmed that.

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

Further, 50 g of the obtained partially crosslinked ethoxyethoxylated polyhydroxystyrene was added to pyridine 3
Of the di-carbonic acid while stirring at 40 ° C.
4.5 g of tert-butyl were 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, dropped into 2 L of water, filtered, and dried in vacuo to obtain a polymer. The obtained polymer was represented by the following chemical 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 chemical formula (Polym. 12) was obtained in the same manner 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
olym. A polymer represented by 13) was obtained.

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

The structure of the obtained polymer was as shown in the following formula, and the substitution ratio of each was as shown in Table 1. In the following formula, R represents the following unit U1 or U2
Represents a cross-linking group which cross-links between molecules or between molecules, and (R)
Indicates a state where the crosslinking group R is bonded.

[0207]

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[0208]

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[0209]

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[0210]

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[0211]

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[0212]

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[0213]

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[0214]

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[0215]

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[0216]

[Table 1] * Polyhydroxystyrene

[Examples and Comparative Examples] The polymer compound (Polym. 1 to 14) obtained in the above synthesis example was used as a base resin,
An acid generator represented by the following formula (PAG.1-12), a dissolution controlling agent represented by the following formula (DRR.1-4), a basic compound, an intramolecular compound represented by the following formula (ACC.1, 2) Nya
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, and a resist having a composition shown in Tables 2 and 3 is obtained. The liquid was prepared. If necessary, use the surfactant Florad “FC-430 (Sumitomo 3M Limited)
0.1 part) was added to improve the film formability.

For comparison, the following chemical formula (Poly
m. A resist solution was prepared with the composition shown in Table 4 in the same manner as described above, using the polymer compound represented by the formulas 15 to 18) as a base resin.

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

Then, exposure was performed by using an excimer laser stepper (Nikon Corporation, NSR-2005EX NA = 0.5) through a mask for forming a target pattern, and baked at 110 ° C. for 90 seconds. 60% aqueous solution of 38% tetramethylammonium hydroxide
After developing for 2 seconds, a positive pattern could be obtained.

The obtained resist pattern was evaluated as follows. First, the sensitivity (Eth) was determined. Then 0.24
μm line and space top and bottom 1: 1
And the minimum line width of the separated line and space at this exposure amount was taken as the resolution of the evaluation resist. The resolution was also observed when the time lapse (PED) from the exposure at the same exposure amount to the heat treatment was 2 hours. The shape of the resolved resist pattern was observed using a scanning electron microscope.
Heating was performed on a hot plate at 0 ° C. for 10 minutes, and a change in pattern shape before and after heating was observed.

Tables 2 to 4 show the resist compositions, Table 5 shows the evaluation results of the examples, and Table 6 shows the evaluation results of the comparative examples.

[0223]

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[0224]

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[0225]

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[0226]

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[0227]

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[0228]

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[0229]

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[0230]

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[0231]

[Table 2]

[0232]

[Table 3]

[0233]

[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 A mixed solution of glycol monomethyl ether acetate (90% by weight) and ethyl pyruvate (10% by weight) PGMEA / CH: A mixed solution of propylene 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)

[0234]

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

[0235]

[Table 6]

Next, Embodiments 21, 22, 23 and 24 described above
Of Surfynol 82 having the following structural formula
Was added so as to be 0.05% by weight of the entire resist composition, and the resist compositions of Comparative Examples 6, 7, 8, and 9 were observed for storage stability with respect to an increase in particles (foreign matter). The results are shown in Table 7 below. At this time, KL-20A (Rion Co., Ltd.) was used as a submerged particle counter.
0.3 μm in an accelerated test by storage at 40 ° C.
The particle size of m was monitored.

[0237]

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[0238]

[Table 7]

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor: ▲ Flag ▼ Tomokin 1-10, Hitomi, Matsuida-cho, Usui-gun, Gunma Prefecture Inside the Silicone Electronic Materials Technology Laboratory, Shin-Etsu Chemical Co., Ltd. (72) Inventor: Yoshifumi Takeda Niigata 28-1 Nishi-Fukushima, Kushiro-mura, Nakakukujo-gun, Japan Shin-Etsu Chemical Industry Co., Ltd. (72) Inventor Shigehiro Nakura 28-1, Nishi-Fukushima, Oku-ku, Nakakushiro-mura, Niigata Prefecture Shin-Etsu Chemical Co., Ltd. 72) Inventor Toshinobu Ishihara 28-1 Nishifukushima, Kazagi-mura, Nakakubijo-gun, Niigata Prefecture Within the Synthetic Technology Research Laboratory, Shin-Etsu Chemical Co., Ltd. 2H025 AA01 AA02 AA04 AA09 AA10 AB16 AC04 AC08 AD03 BE00 BE10 BG00 CC02 CC03 CC20 FA01 FA03 FA12 FA17 2H096 AA25 BA11 BA20 DA01 EA05 FA01 GA 08 JA02 JA03

Claims (17)

[Claims] (A): Organic solvent (B): One or more acid labile as base resin
Group-containing polymer compound is further intramolecular and / or intermolecular.
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): containing an acid generator, wherein the base resin has the following general formula
A weight-average molecule having a repeating unit represented by (1 ')
High molecular compound having an amount of 1,000 to 500,000
Alkenyl represented by the following general formula (I) or (II)
A compound represented by the following general formula (5a):
The following general formula (3) obtained by reacting the compound
Polymers represented by a'-1) and / or (3a'-2)
Chemically amplified positive resist characterized by being a compound
material. Embedded imageEmbedded image(Where R¹Represents a hydrogen atom or a methyl group;^TwoIs carbon
Represents a linear, branched or cyclic alkyl group of the formulas 1 to 8
You. Further, x is 0 or a positive integer, y is a positive integer,
It is a number that satisfies x + y ≦ 5. R^Four, R^FiveIs a hydrogen atom or
Is a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms
And R⁶Has a heteroatom having 1 to 18 carbon atoms.
A monovalent hydrocarbon group which may be^FourAnd R^Five, R^FourWhen
R⁶, R^FiveAnd R⁶May form a ring or form a ring
R in case^Four, R^Five, R⁶Are straight-chains each having 1 to 18 carbon atoms.
It represents a chain or branched alkylene group. R^4aIs a hydrogen atom
Or a linear, branched or cyclic alkyl having 1 to 7 carbon atoms
A group represented by R^4a-CH and R^FiveOr R^{Four a}-CH and R⁶Is a ring
May be formed, and when forming a ring, R^4a-CH
Is R ^4a-CH_TwoR represented by^FourIs linear having 1 to 18 carbon atoms
Or a group that becomes a branched alkylene group;^Five, R⁶Is
Represents a linear or branched alkylene group having 1 to 18 carbon atoms
You. Q represents the following general formula (4a) or (4b):R represents a group represented by⁸, R⁹Is a hydrogen atom or carbon number 1
And represents a linear, branched or cyclic alkyl group of from 8 to 8. or
Is R⁸And R⁹May form a ring, and may form a ring
R if⁸, R⁹Is a straight or branched chain having 1 to 8 carbon atoms.
Represents a alkylene group. R^8aIs a hydrogen atom or a group having 1 to 7 carbon atoms
A linear, branched or cyclic alkyl group;^8a-C
H and R⁹And may form a ring, and when forming a ring,
Is R^8a-CH is R^8a-CH_TwoR represented by⁸Has 1 carbon
Represents a group which becomes a linear or branched alkylene group
Then R⁹Is a linear or branched alkylene having 1 to 8 carbon atoms
Shows a substituent group. R¹³Is linear or branched having 1 to 10 carbon atoms
And d is 0 or an integer of 1 to 10. A
Is a c-valent aliphatic or alicyclic saturated carbon atom having 1 to 50 carbon atoms.
A hydrocarbon group, an aromatic hydrocarbon group or a heterocyclic group,
These groups may have heteroatoms interposed and
Some of the hydrogen atoms bonded to the carbon atoms of the
Substituted by a xyl, carbonyl or fluorine atom
It may be. B is -CO-O-, -NHCO-O-
Or -NHCONH-. c is 2 to 8, c 'is 1 to
It is an integer of 7. m is 0 or a positive integer, n is a positive integer
And m + n = y. p1 and p2 are positive numbers, q11 and q
12 is a positive number, and 0 <p1 / (p1 + q11 + q12
+ P2) ≦ 0.8, 0 <q11 / (p1 + q11 + q1)
2 + p2) ≦ 0.8, 0 <q12 / (p1 + q11 + q
12 + p2) ≦ 0.8, p1 + q11 + q12 + p2 =
It is a number that satisfies 1. ) (A): an organic solvent (B): a polymer compound having one or more acid labile groups as a base resin further comprises a C—O—C group within and / or between molecules. A polymer compound having a weight average molecular weight of 1,000 to 500,000 cross-linked by a cross-linking group having the formula (C): an acid generator, wherein the base resin is represented by the following general formula (1 ′) A polymer compound having a repeating unit represented by the formula and having a weight average molecular weight of 1,000 to 500,000 is added to a halogenated alkyl ether compound represented by the following general formula (VI) or (VII); 5
a chemically amplified positive resist characterized by being a polymer compound represented by the following general formula (3a'-1) and / or (3a'-2) obtained by reacting the compound represented by b): material. Embedded image Embedded image (Wherein, 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 A positive integer,
It is a number that satisfies x + y ≦ 5. R ⁴ and R ^{5 each} represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, and R ⁶ represents a monovalent group which may have a heteroatom having 1 to 18 carbon atoms. R ⁴ and R ⁵ , R ⁴ and R ⁶ , R ⁵ and R ⁶ may form a ring, and when forming a ring, R ⁴ , R ⁵ and R ⁶ each represent a hydrocarbon group; It represents a linear or branched alkylene group having 1 to 18 carbon atoms. Z represents a halogen atom. Q is the following general formula (4a) or (4b): Wherein R ⁸ and R ⁹ are a hydrogen atom or a carbon atom
And represents a linear, branched or cyclic alkyl group of 1 to 8. Alternatively, R ⁸ and R ⁹ may form a ring, and when forming a ring, R ⁸ and R ^{9 each} represent a linear or branched alkylene group having 1 to 8 carbon atoms. R ¹³ is a linear or branched alkylene group having 1 to 10 carbon atoms, and d is 0 or an integer of 1 to 10. A represents a c-valent aliphatic or alicyclic saturated hydrocarbon group having 1 to 50 carbon atoms, an aromatic hydrocarbon group or a heterocyclic group, and these groups may have a hetero atom interposed;
Some of the hydrogen atoms bonded to the carbon atoms are hydroxyl groups,
It may be substituted by a carboxyl group, a carbonyl group or a fluorine atom. B is -CO-O-, -NHCO
-O- or -NHCONH- is shown. c is 2 to 8, c '
Is an integer of 1 to 7. m is 0 or a positive integer, n is a positive integer, and m + n = y. p1 and p2 are positive numbers, q1
1, q12 are positive numbers, and 0 <p1 / (p1 + q11 +
q12 + p2) ≦ 0.8, 0 <q11 / (p1 + q11)
+ Q12 + p2) ≦ 0.8, 0 <q12 / (p1 + q1)
1 + q12 + p2) ≦ 0.8, p1 + q11 + q12 +
This is a number that satisfies p2 = 1. ) 3. As a base resin, an acid labile group represented by the following general formula (6) is added to a phenolic hydroxyl group of a polymer compound represented by the formula (3a′-1) and / or (3a′-2): 3. The resist material according to claim 1, wherein a polymer compound having q2 mol of a tert-alkyl group, a trialkyl group or a ketoalkyl group introduced therein is used. Embedded image (In the formula, R ⁷ represents a tertiary alkyl group having 4 to 12 carbon atoms. A is an integer of 0 to 6.) 4. An acid labile group represented by the above formula (6) is introduced as a base resin into a phenolic hydroxyl group of a polymer compound represented by the formula (3a′-1) and / or (3a′-2). The following general formula (3b′-1) or (3b′-2)
4. The resist material according to claim 3, wherein a polymer compound represented by the following formula is used. Embedded image (Wherein, R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ , R ⁷ , Q, x, y,
m, n, a, p1, p2, q11, and q12 have the same meaning as described above. ) (A): an organic solvent (B): a polymer compound having one or more acid labile groups as a base resin further comprises a C—O—C group within and / or between molecules. A polymer compound having a weight average molecular weight of 1,000 to 500,000 cross-linked by a cross-linking group having the formula (C): an acid generator, wherein the base resin is represented by the following general formula (1 ′) A polymer having a repeating unit represented by the formula and having a weight average molecular weight of 1,000 to 500,000 is added to an alkenyl ether compound represented by the following general formula (I) or (II) or a compound represented by the following general formula (VI) or The following general formula (3c ′) obtained by reacting a halogenated alkyl ether compound represented by (VII)
A chemically amplified positive resist material characterized by being a polymer compound represented by -1) and / or (3c'-2). Embedded image Embedded image (Wherein, 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 A positive integer,
It is a number that satisfies x + y ≦ 5. Q is the following general formula (4
a) or (4b) Wherein R ⁸ and R ⁹ are a hydrogen atom or a carbon atom
And represents a linear, branched or cyclic alkyl group of 1 to 8. Alternatively, R ⁸ and R ⁹ may form a ring, and when forming a ring, R ⁸ and R ^{9 each} represent a linear or branched alkylene group having 1 to 8 carbon atoms. R ^8a represents a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 7 carbon atoms, and R ^8a -C
The H and R ⁹ may form a ring, when they form a ring, R ^8a -CH is R ⁸ is a carbon number 1 represented by R ^8a -CH ₂
And R ⁹ represents a linear or branched alkylene group having 1 to 8 carbon atoms. R ¹³ is a linear or branched alkylene group having 1 to 10 carbon atoms, and d is 0 or an integer of 1 to 10. A
Represents a c-valent aliphatic or alicyclic saturated hydrocarbon group having 1 to 50 carbon atoms, an aromatic hydrocarbon group or a heterocyclic group,
In these groups, a hetero atom may be interposed, and a part of the hydrogen atom bonded to the carbon atom may be substituted by a hydroxyl group, a carboxyl group, a carbonyl group or a fluorine atom. B is -CO-O-, -NHCO-O-
Or -NHCONH-. c is 2-8, c 'is 1
It is an integer of 7. m is 0 or a positive integer, n is a positive integer, and m + n = y. p1 and p2 are positive numbers, q11 and q
12 is a positive number, and 0 <p1 / (p1 + q11 + q12
+ P2) ≦ 0.8, 0 <q11 / (p1 + q11 + q1)
2 + p2) ≦ 0.8, 0 <q12 / (p1 + q11 + q
12 + p2) ≦ 0.8, p1 + q11 + q12 + p2 =
It is a number that satisfies 1. ) 6. As a base resin, an acid labile group represented by the following general formula (6) is added to a phenolic hydroxyl group of a polymer compound represented by the formula (3a′-1) and / or (3a′-2): 6. The resist material according to claim 5, wherein a polymer compound having q2 mol of a tert-alkyl group, a trialkyl group or a ketoalkyl group introduced therein is used. Embedded image (In the formula, R ⁷ represents a tertiary alkyl group having 4 to 12 carbon atoms. A is an integer of 0 to 6.) 7. As a base resin, an acid labile group represented by the following general formula (5) is added to a phenolic hydroxyl group of a polymer compound represented by the formula (3a′-1) and / or (3a′-2). 7. The resist material according to claim 5, wherein a polymer compound introduced by q1 mol is used. Embedded image (Wherein R ⁴ and R ⁵ represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, and R ⁶ may have a heteroatom having 1 to 18 carbon atoms. R ⁴ and R ⁵ , R ⁴ and R ⁶ , R ⁵ and R ⁶ may form a ring, and when forming a ring, R ⁴ and R ⁵ , R ⁶ represents a linear or branched alkylene group having 1 to 18 carbon atoms.) 8. The resist material according to claim 1, wherein an onium salt and / or a diazomethane derivative is blended as the component (C). 9. The resist material according to claim 1, wherein a basic compound is blended as the component (D). 10. The resist material according to claim 9, wherein an aliphatic amine is blended as the component (D). 11. The method according to claim 11, wherein the component (C) is ≡C—CO
The resist material according to any one of claims 1 to 10, further comprising an aromatic compound having a group represented by OH. Further, as a base resin different from 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) may be used. A polymer compound having a weight average molecular weight of 3,000 to 300,000 partially substituted by two or more acid labile groups at a ratio of 0 to 80 mol% on average as a whole. 12. The resist material according to any one of 1 to 11. Embedded image (Wherein, 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 A positive integer,
It is a number that satisfies x + y ≦ 5. ) 13. A component represented by the following general formula (1):
The weight average molecular weight having the repeating unit represented by 0) is
Contains 3,000 to 300,000 high molecular compounds
The resist material according to claim 12, wherein: Embedded image(Where R¹, R^Two, R^Four, R^Five, R⁶Is the same as above
And R¹⁴Is -CR^FourR ^FiveOR⁶Acid labile groups different from
Where e and f are 0 or positive numbers, g is a positive number, and e + f + g
= 1, 0 ≦ e / (e + f + g) ≦ 0.5, 0.4
≦ g / (e + f + g) ≦ 0.9. ) 14. The resist material according to claim 1, further comprising (G) a dissolution controlling agent. 15. The resist material according to claim 1, further comprising (H) an ultraviolet absorber. 16. The resist material according to claim 1, further comprising (I): an acetylene alcohol derivative. (I) any one of claims 1 to 16
(Ii) a step of applying a chemically amplified positive resist material as described in (1) above on a substrate; (ii) exposing with a high-energy ray or an electron beam having a wavelength of 300 nm or less through a photomask after a heat treatment; And b.) Performing a heat treatment as needed, and then developing with a developer.