JP2001324814A - Chemical amplification type resist material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a chemical amplification positive type resist material having a higher dry etching resistance than a conventional resist material, also having high sensitivity, high resolution and process adaptability and ensuring a suppressed thickness reduction of a pattern after development with an aqueous alkali solution by adding both a polyhydroxystyrene derivative and a copolymer of hydroxystyrene and a (meth)acrylic ester, particularly a three- component copolymer as a base resin to a resist material. SOLUTION: The chemical amplification type resist material contains a high molecular mixture of a high molecular compound having repeating units of formula (1) and an Mw of 1,000-500,000 with a high molecular compound having repeating units of formula (2) and an Mw of 1,000-500,000.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a chemically amplified positive resist material such as a chemically amplified positive resist material having high sensitivity and high resolution and particularly suitable 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 increasing and the pattern rules have been required to be finer, far-ultraviolet rays, EB, EUV, and X-ray lithography are promising as next-generation fine processing techniques. 0.24 for deep ultraviolet lithography
Processing of μm or less is possible, and when a resist material having low light absorption is used, a pattern having side walls nearly perpendicular to the substrate can be formed.

A recently developed acid-catalyzed chemically amplified positive resist material (described in Japanese Patent Publication No. 2-27660 and Japanese Patent Application Laid-Open No. 63-27829) is a highly luminous KrF excimer as a light source for far ultraviolet rays. Using a laser, sensitivity,
It is expected to be a particularly promising resist material for deep-ultraviolet lithography having high resolution and dry etching resistance and excellent characteristics.

As such a chemically amplified positive resist material, a two-component system comprising a base polymer and an acid generator, and a three-component system comprising a base polymer, an acid generator and a dissolution controlling agent having an acid labile group are available. Are known.

For example, Japanese Patent Application Laid-Open No. Sho 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.
Reduction of pattern thickness after development with alkaline aqueous solution,
There are drawbacks such as low resistance to dry etching.

A resist material using a copolymer of hydroxystyrene and (meth) acrylate has also been reported in order to achieve higher transparency and adhesion to a substrate (Japanese Patent Application Laid-Open No. H8-101509). JP-A-8-14
No. 6610), this type of resist material has problems such as heat resistance, partial pattern collapse, and footing in the pattern shape.

[0008] The present invention has been made in view of the above circumstances,
Dry etching resistance, better than conventional resist materials
An object of the present invention is to provide a chemically amplified resist material having high sensitivity, high resolution, process adaptability, and having an improved reduction in pattern film thickness after development with an alkaline aqueous solution.

[0009]

Means for Solving the Problems and Embodiments of the Invention The present inventors have made intensive studies to achieve the above object, and as a result, the weight average molecular weight having a repeating unit represented by the following general formula (1) is 1 And a weight average molecular weight having a repeating unit represented by the following general formula (2) of 1,000 to 500,000.
It is effective as a base resin of a chemically amplified positive resist material to be used in combination with a polymer compound of 0, and a chemically amplified positive resist material containing a mixture of the polymer compound, an acid generator, and an organic solvent, It has excellent dry etching resistance, high sensitivity and resolution, and process adaptability, improves the reduction in pattern thickness after development with an alkaline aqueous solution, has high practicality, and is advantageously used for precision fine processing. Has found that it is very effective as a resist material for VLSI.

[0010]

Embedded image(Wherein R is a hydroxyl group or OR^ThreeA group represented by R¹Is a hydrogen atom
Or a methyl group; ^TwoIs a straight chain having 1 to 8 carbon atoms,
A branched or cyclic alkyl group;^Three, R^FourIs acid labile
A group represented by R^FiveRepresents a methyl group or an ethyl group. Z is charcoal
A linear, branched or cyclic alkylene group having a prime number of 1 to 10
Is shown. X is 0 or a positive integer, and y is a positive integer.
Is a number satisfying x + y ≦ 5, and m is 0 or a positive integer.
Is a number, n is a positive integer and satisfies m + n ≦ 5
Is a number. p, q, r, and s are 0 or a positive number, and p + q
It is a number that satisfies + r + s = 1. )

[0011]

Embedded image (Wherein, R ⁶ , R ⁷ , and R ⁸ represent a hydrogen atom or a methyl group, R ⁹ represents a methyl group or an ethyl group, and E has 1 carbon atom.
Represents 10 to 10 linear, branched or cyclic alkylene groups. R ¹⁰ represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms containing an oxygen atom or a sulfur atom. R ¹¹ represents a tertiary alkyl group having 1 to 20 carbon atoms. k
Is 0 or a positive integer, and is a number satisfying k ≦ 5.
t and w are positive numbers, and u and v are 0 or positive numbers,
One of u and v is not 0, and t + u + v + w =
It is a number that satisfies 1. )

As described above, when the high molecular compounds represented by the above general formulas (1) and (2) are used together in a resist material, a great effect is obtained beyond compensating the disadvantages of the resist materials of both high molecular compounds. Has advantages. That is, when only the polymer compound represented by the general formula (1) is used as a resist material, it has high sensitivity and high resolution, but has poor resistance to dry etching, and has a pattern after development with an alkaline aqueous solution. This has the disadvantage that the thickness of the film decreases greatly. On the other hand, when only the polymer compound represented by the above general formula (2) is used as a resist material, it has the advantages of strong dry etching resistance and a relatively small decrease in the pattern film thickness after development with an alkaline aqueous solution. However, the sensitivity is low, and disadvantages such as skirting in the pattern shape also appear.

On the other hand, when the polymer compounds represented by the above general formulas (1) and (2) are used together in a resist material, higher sensitivity and higher resolution are obtained than when only one of them is used. , Has process adaptability, and has excellent dry etching resistance, and the decrease in pattern film thickness after development with an alkaline aqueous solution is relatively small.
The inventors of the present invention have found that a chemically amplified positive resist material can be obtained, and have accomplished the present invention.

Hereinafter, the present invention will be described in more detail. The chemically amplified resist material of the present invention has a weight average molecular weight of 1,000 to 500,000 having a repeating unit represented by the following general formula (1). A polymer compound;
It is characterized by containing both high molecular compounds having a weight average molecular weight of 1,000 to 500,000 having a repeating unit represented by the following general formula (2).

[0015]

Embedded image(Wherein R is a hydroxyl group or OR^ThreeA group represented by R¹Is a hydrogen atom
Or a methyl group; ^TwoIs a straight chain having 1 to 8 carbon atoms,
A branched or cyclic alkyl group;^Three, R^FourIs acid labile
A group represented by R^FiveRepresents a methyl group or an ethyl group. Z is charcoal
A linear, branched or cyclic alkylene group having a prime number of 1 to 10
Is shown. X is 0 or a positive integer, and y is a positive integer.
Is a number satisfying x + y ≦ 5, and m is 0 or a positive integer.
Is a number, n is a positive integer and satisfies m + n ≦ 5
Is a number. p, q, r, and s are 0 or a positive number, and p + q
It is a number that satisfies + r + s = 1. )

Here, the linear, branched or cyclic alkyl group includes a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group and a tert-
Examples thereof include a butyl group, a cyclopentyl group, and a cyclohexyl group.

The acid labile groups of R ³ and R ⁴ are variously selected, and in particular, groups represented by the following formulas (3) and (4), and branched or cyclic tricyclic groups having 4 to 20 carbon atoms. It is preferable that the lower alkyl group and each alkyl group be a trialkylsilyl group having 1 to 6 carbon atoms and an oxoalkyl group having 4 to 20 carbon atoms, respectively. The acid labile groups of R ³ and R ⁴ are different from each other.

[0018]

Embedded image

In the formula (3), R ¹² and R ^{13 each} represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms. , Ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, cyclopentyl, cyclohexyl, 2-ethylhexyl, n-octyl and the like. R ¹⁴ has 1 to 1 carbon atoms
18, preferably a monovalent hydrocarbon group which may have a hetero atom such as 1 to 10 oxygen atoms, such as a linear, branched or cyclic alkyl group. Examples thereof include those partially substituted with a hydroxyl group, an alkoxy group, an oxo group, an amino group, an alkylamino group, and the like, and specific examples include the following substituted alkyl groups.

[0020]

Embedded image

R ¹² and R ¹³ , R ¹² and R ¹⁴ , R ¹³ and R ¹⁴ may form a ring, and when forming a ring, R ¹² ,
R ¹³ and R ¹⁴ each have 1 to 18 carbon atoms, preferably 1 to
And 10 linear or branched alkylene groups.

In the formula (4), R ¹⁵ and R ¹⁶ are the same as those described for R ¹² and R ¹³ . As the organic group having 4 to 40 carbon atoms for R ¹⁷ , a linear group having 4 to 40 carbon atoms,
A branched or cyclic alkyl group, particularly a tertiary alkyl group having 4 to 20, preferably 4 to 15 carbon atoms, each alkyl group being a trialkylsilyl group having 1 to 6 carbon atoms,
Oxoalkyl group to -20 or a group represented by the above general formula (3);
rt-butyl group, tert-amyl group, 1,1-diethylpropyl group, 1-methylcyclopentyl group, 1-ethylcyclopentyl group, 1-isopropylcyclopentyl group, 1-butylcyclopentyl group, 1-methylcyclohexyl group, 1- Ethylcyclohexyl group, 1-isopropylcyclohexyl group, 1-butylcyclohexyl group,
1-ethyl-2-cyclopentenyl group, 1-ethyl-2
-Cyclohexenyl group, 2-methyl-2-adamantyl group, and the like, and specific examples of the trialkylsilyl group include a trimethylsilyl group, a triethylsilyl group, a dimethyl-tert-butylsilyl group, and the like, and an oxoalkyl group. Specifically, a 3-oxocyclohexyl group, a 4-methyl-2-oxooxan-4-yl group, 5
-Methyl-2-oxooxolan-5-yl group and the like. a is an integer of 0 to 6.

Specific examples of the linear or branched acid labile group represented by the above formula (3) include the following groups.

[0024]

Embedded image

As the cyclic group among the acid labile groups represented by the above formula (3), specifically, tetrahydrofuran-
Examples thereof include a 2-yl group, a 2-methyltetrahydrofuran-2-yl group, a tetrahydropyran-2-yl group, and a 2-methyltetrahydropyran-2-yl group.

Specific examples of the acid labile group of the above formula (4) include a tert-butoxycarbonyl group, a tert-butoxycarbonylmethyl group, a tert-amyloxycarbonyl group, a tert-amyloxycarbonylmethyl group,
1,1-diethylpropyloxycarbonyl group, 1,1
-Diethylpropyloxycarbonylmethyl group, 1-ethylcyclopentyloxycarbonyl group, 1-ethylcyclopentyloxycarbonylmethyl group, 1-ethyl-
2-cyclopentenyloxycarbonyl group, 1-ethyl-2-cyclopentenyloxycarbonylmethyl group, 1
-Ethoxyethoxycarbonylmethyl group, 2-tetrahydropyranyloxycarbonylmethyl group, 2-tetrahydrofuranyloxycarbonylmethyl group and the like.

Further, the carbon number is 4-20, preferably 4-1.
The tertiary alkyl group of 5 includes a tert-butyl group, t
tert-amyl group, tert-ethyl-3-pentyl group, dimethylbenzyl group and the like, and 1-methylcyclopentyl, 1-ethylcyclopentyl, 1-n
-Propylcyclopentyl, 1-isopropylcyclopentyl, 1-n-butylcyclopentyl, 1-sec-
Butylcyclopentyl, 1-methylcyclohexyl, 1
-Ethylcyclohexyl, 3-methyl-1-cyclopenten-3-yl, 3-ethyl-1-cyclopentene-3
-Yl, 3-methyl-1-cyclohexen-3-yl,
Examples thereof include 3-ethyl-1-cyclohexen-3-yl.

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

[0029]

Embedded image

In the above formula (1), p, q,
r and s are 0 or positive numbers, especially p, q and r are positive numbers,
s is 0 or a positive number, p + q + r + s = 1, 0 <(q +
r) / (p + q + r + s) ≦ 0.8, especially 0.07 ≦
(Q + r) / (p + q + r + s) ≦ 0.5, 0.01 ≦
s / (p + q + r + s) ≦ 0.1, especially 0.01 ≦ s /
It is preferable to satisfy (p + q + r + s) ≦ 0.05. When any of p, q, and r becomes 0, the contrast of the alkali dissolution rate decreases, and the resolution deteriorates.
If the ratio of q + r to the whole exceeds 0.8, or if the total ratio of s to the whole exceeds 0.1, the gel is excessively crosslinked and loses solubility in alkali,
In the case of alkali development, a change in film thickness, stress in the film or generation of air bubbles may be caused, or adhesion to the substrate may be poor due to a decrease in the number of hydrophilic groups. Further, by appropriately selecting the values of p, q, and r within the above range, the dimension of the pattern and the shape of the pattern can be arbitrarily controlled.

In the polymer compound of the present invention, the content of the acid labile group affects the contrast of the dissolution rate of the resist film, and affects the characteristics of the resist material such as pattern dimension control and pattern shape.

In the polymer compound having a repeating unit of the formula (1) of the present invention, the acid labile groups of R ³ and R ⁴ are particularly preferably those represented by the above formulas (3) and (4).
Further, each unit constituting the above repeating unit may be one kind or a combination of two or more kinds.

[0033]

Embedded image (Wherein, R ⁶ , R ⁷ , and R ⁸ represent a hydrogen atom or a methyl group, R ⁹ represents a methyl group or an ethyl group, and E has 1 carbon atom.
Represents 10 to 10 linear, branched or cyclic alkylene groups. R ¹⁰ represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms containing an oxygen atom or a sulfur atom. R ¹¹ represents a tertiary alkyl group having 1 to 20 carbon atoms. k
Is 0 or a positive integer, and is a number satisfying k ≦ 5.
t and w are positive numbers, and u and v are 0 or positive numbers,
One of u and v is not 0, and t + u + v + w =
It is a number that satisfies 1. )

As the acid labile group for R ¹¹ , various groups are selected, and groups represented by the following formulas (5) and (6) are particularly preferred.

[0035]

Embedded image (In the formula, R ¹⁸ is a methyl group, an ethyl group, an isopropyl group, a cyclohexyl group, a cyclopentyl group, a vinyl group, an acetyl group, a phenyl group, or a cyano group, and b is an integer of 0 to 3.)

As the cyclic alkyl group of the formula (5), a 5-membered ring is more preferred. Specific examples include 1-methylcyclopentyl, 1-ethylcyclopentyl, 1-isopropylcyclopentyl, 1-vinylcyclopentyl, 1-acetylcyclopentyl, 1-phenylcyclopentyl,
Examples thereof include 1-cyanocyclopentyl, 1-methylcyclohexyl, 1-ethylcyclohexyl, 1-isopropylcyclohexyl, 1-vinylcyclohexyl, 1-acetylcyclohexyl, 1-phenylcyclohexyl, 1-cyanocyclohexyl, and the like.

[0037]

Embedded image (However, in the formula, R ¹⁹ is an isopropyl group, a cyclohexyl group, a cyclopentyl group, a vinyl group, an acetyl group, a phenyl group, or a cyano group.)

Specific examples of the formula (6) include 1-vinyldimethyl, 1-acetyldimethyl, 1-phenyldimethyl, 1-cyanodimethyl and the like.

The alkyl group for R ¹⁰ is selected from various types. Specific examples include cyclohexyl, cyclopentyl, norbornyl, isobornyl, 5-membered lactone, 6-membered lactone, tetrahydrofuran, and carbonate groups. , Dioxolane group, hydroxyethyl group,
Examples include, but are not limited to, an alkyl group substituted with a methoxymethyl group.

Further, considering the characteristics of the resist material,
t and w are positive numbers, and u and v are 0 or positive numbers, respectively.
One of u and v is not 0, and preferably satisfies the following expression.

0 <w / (t + u + v + w) ≦ 0.5, more preferably 0.2 <w / (t + u + v + w) ≦ 0.4
It is. 0 ≦ v / (t + u + v + w) ≦ 0.2, more preferably 0.01 <v / (t + u + v + w) ≦ 0.1. 0 ≦ u / (t + u + v + w) ≦ 0.05, more preferably 0 ≦ u / (t + u + v + w) ≦ 0.02.

When w becomes 0 and the polymer compound of the above formula (2) does not contain this unit, the contrast of the alkali dissolution rate decreases and the resolution deteriorates. On the other hand, if the proportion of t is too large, the alkali dissolution rate of the unexposed portion becomes too high. Even when both u and v are 0, disadvantages such as poor resolution and poor dry etching resistance appear. By appropriately selecting the values of t, u, v, and w within the above ranges, the dimension control of the pattern and the shape control of the pattern can be arbitrarily performed.

The polymer compounds of the formulas (1) and (2) of the present invention each have a weight average molecular weight of 1,000 to 500,0.
00, preferably 3,000 to 30,000. If the weight average molecular weight is too small, the resist material will be inferior in heat resistance. If it is too large, the alkali solubility will decrease, and the tailing phenomenon will easily occur after pattern formation.

Further, in the polymer compound of the present invention,
When the molecular weight distribution (Mw / Mn) of the polyhydroxystyrene and (meth) acrylate copolymer used is wide, it is difficult to design the number of crosslinks due to the presence of low molecular weight or high molecular weight polymers, and the same performance In some cases, it becomes difficult to manufacture a resist material having the following. Therefore, as the pattern rule becomes finer, the influence of such molecular weight and molecular weight distribution is likely to increase, so that to obtain a resist material suitably used for fine pattern dimensions,
It is preferable that the molecular weight distribution of the copolymer of hydroxystyrene and (meth) acrylate used is 1.0 to 2.0, particularly 1.0 to 1.5, which is a narrow dispersion.

The mixture of the high molecular compounds of the formulas (1) and (2) of the present invention is effective as a base polymer of a chemically amplified positive resist material. Provide a chemically amplified positive resist material. I. (A) Organic solvent (B) A chemically amplified positive resist material comprising a polymer mixture of general formulas (1) and (2) as a base resin, and (C) an acid generator. II. (A) Organic solvent (B) Chemical amplification characterized by comprising a polymer mixture of general formulas (1) and (2) as base resin (C) Acid generator (D) Dissolution control agent Positive resist material. III. (E) The chemically amplified positive resist composition according to I or II, further comprising a basic compound as an additive.

In the chemically amplified positive resist composition of the present invention, the organic solvent of the component (A) includes butyl acetate, amyl acetate, cyclohexyl acetate, 3-methoxybutyl acetate, methyl ethyl ketone, methyl amyl ketone, cyclohexanone, and cyclopentanone. 3-ethoxyethyl propionate, 3-ethoxymethyl propionate, 3
-Methoxymethyl propionate, methyl acetoacetate,
Ethyl acetoacetate, diacetone alcohol, methyl pyruvate, ethyl pyruvate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, ethylene glycol monomethyl ether, ethylene Glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 3-methyl-3-methoxybutanol, N-methylpyrrolidone, dimethyl sulfoxide, γ-butyrolactone, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether Acetate, lactate , Lactate, ethyl lactate, propyl,
Examples include, but are not limited to, tetramethylene sulfone. Particularly preferred are propylene glycol alkyl ether acetate and alkyl lactate. These solvents may be used alone or in combination of two or more. Examples of preferred mixed solvents are propylene glycol alkyl ether acetate and alkyl lactate. In the present invention, the alkyl group of the propylene glycol alkyl ether acetate has 1 carbon atom.
To 4, for example, a methyl group, an ethyl group, and a propyl group. Among them, a methyl group and an ethyl group are preferable. The propylene glycol alkyl ether acetate includes a 1,2-substituted product and a 1,3-substituted product, and there are three types of isomers depending on the combination of substitution positions. However, they may be used alone or in a mixture.

The alkyl group of the above-mentioned alkyl lactate has 1 to 4 carbon atoms, such as a methyl group, an ethyl group and a propyl group. Among them, a methyl group and an ethyl group are preferred.

When propylene glycol alkyl ether acetate is added as a solvent, 5
It is preferably at least 0% by weight, and when adding the alkyl lactate, it is preferably at least 50% by weight based on the total solvent. When a mixed solvent of propylene glycol alkyl ether acetate and alkyl lactate is used as a solvent, the total amount is preferably 50% by weight or more based on the total solvent. In this case, the proportion of propylene glycol alkyl ether acetate is more preferably 60 to 95% by weight, and the proportion of alkyl lactate is 5 to 40% by weight.
When the amount of propylene glycol alkyl ether acetate is small, there is a problem such as deterioration of coating properties, and when too large, there is a problem of insufficient solubility and generation of particles and foreign matters. When the amount of the alkyl lactate is too small, there are problems such as insufficient solubility, increase of particles and foreign substances, and when too much, there is a problem that the viscosity becomes high, the coating property is deteriorated, and the storage stability is deteriorated.

The amount of these solvents to be added is 300 to 2.0% based on 100 parts by weight of the solid content of the chemically amplified positive resist composition.
The amount is 00 parts by weight, preferably 400 to 1,000 parts by weight, but is not limited to this as long as the concentration can be achieved by an existing film forming method.

As the photoacid generator as the component (C), any compound can be used as long as it generates an acid upon irradiation with high energy rays. Suitable photoacid generators include sulfonium salts, iodonium salts, sulfonyldiazomethane, N-
There are sulfonyloxyimide type acid generators and the like. As described in detail below, these can be used alone or in combination of two or more.

The sulfonium salt is a salt of a sulfonium cation and a sulfonate. As the sulfonium cation, triphenylsulfonium, (4-tert-butoxyphenyl) diphenylsulfonium, bis (4-ter
t-butoxyphenyl) phenylsulfonium, tris (4-tert-butoxyphenyl) sulfonium,
(3-tert-butoxyphenyl) diphenylsulfonium, bis (3-tert-butoxyphenyl) phenylsulfonium, tris (3-tert-butoxyphenyl) sulfonium, (3,4-ditert-butoxyphenyl) diphenylsulfonium, bis ( 3,4-
Di-tert-butoxyphenyl) phenylsulfonium, tris (3,4-ditert-butoxyphenyl)
Sulfonium, diphenyl (4-thiophenoxyphenyl) sulfonium, (4-tert-butoxycarbonylmethyloxyphenyl) diphenylsulfonium, tris (4-tert-butoxycarbonylmethyloxyphenyl) sulfonium, (4-tert-butoxyphenyl) bis ( 4-dimethylaminophenyl) sulfonium, tris (4-dimethylaminophenyl) sulfonium, 2-naphthyldiphenylsulfonium, dimethyl 2-naphthylsulfonium, 4-hydroxyphenyldimethylsulfonium, 4-methoxyphenyldimethylsulfonium, trimethylsulfonium, 2-oxo Cyclohexylcyclohexylmethylsulfonium, trinaphthylsulfonium, tribenzylsulfonium and the like; Examples of trifluoromethanesulfonate, nonafluorobutanesulfonate, heptadecafluorooctanesulfonate, 2,2,2-trifluoroethanesulfonate, pentafluorobenzenesulfonate, 4-trifluoromethylbenzenesulfonate, 4-fluorobenzenesulfonate, toluene Examples thereof include sulfonate, benzenesulfonate, 4- (4-toluenesulfonyloxy) benzenesulfonate, naphthalenesulfonate, camphorsulfonate, octanesulfonate, dodecylbenzenesulfonate, butanesulfonate, and methanesulfonate.

The iodonium salt is a salt of an iodonium cation and a sulfonate, such as diphenyliodonium, bis (4-tert-butylphenyl) iodonium,
-Tert-butoxyphenylphenyliodonium,
Aryliodonium cations such as 4-methoxyphenylphenyliodonium and sulfonates as trifluoromethanesulfonate, nonafluorobutanesulfonate, heptadecafluorooctanesulfonate,
2,2-trifluoroethanesulfonate, pentafluorobenzenesulfonate, 4-trifluoromethylbenzenesulfonate, 4-fluorobenzenesulfonate, toluenesulfonate, benzenesulfonate,
-(4-toluenesulfonyloxy) benzenesulfonate, naphthalenesulfonate, camphorsulfonate, octanesulfonate, dodecylbenzenesulfonate, butanesulfonate, methanesulfonate and the like, and an iodonium salt of these combinations.

Examples of the sulfonyldiazomethane include bis (ethylsulfonyl) diazomethane, bis (1-methylpropylsulfonyl) diazomethane, bis (2-methylpropylsulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, bis (cyclohexyl) Sulfonyl) diazomethane, bis (perfluoroisopropylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, bis (4-methylphenylsulfonyl) diazomethane, bis (2,4-dimethylphenylsulfonyl) diazomethane, bis (2-naphthylsulfonyl) diazomethane , 4-methylphenylsulfonylbenzoyldiazomethane, tert-butylcarbonyl-4-methylphenylsulfonyldiazomethane, 2-naphthylsul Sulfonyl benzoyl diazomethane,
4-methylphenylsulfonyl-2-naphthoyldiazomethane, methylsulfonylbenzoyldiazomethane, t
bis-sulfonyldiazomethane, such as ert-butoxycarbonyl-4-methylphenylsulfonyldiazomethane; and sulfonylcarbonyldiazomethane.

Examples of the N-sulfonyloxyimide type photoacid generator include succinimide, naphthalenedicarboxylic acid imide, phthalic acid imide, cyclohexyldicarboxylic acid imide, 5-norbornene-2,3-dicarboxylic acid imide, and 7-oxabicycloimide. [2.2.1] imide skeleton such as -5-heptene-2,3-dicarboxylic imide and trifluoromethanesulfonate, nonafluorobutanesulfonate, heptadecafluorooctanesulfonate;
2,2,2-trifluoroethanesulfonate, pentafluorobenzenesulfonate, 4-trifluoromethylbenzenesulfonate, 4-fluorobenzenesulfonate, toluenesulfonate, benzenesulfonate, naphthalenesulfonate, camphorsulfonate, octanesulfonate, dodecylbenzenesulfonate, butane Compounds of a combination such as sulfonate and methanesulfonate are exemplified.

Benzoin sulfonate type photoacid generators include benzoin tosylate, benzoin mesylate,
Benzoin butane sulfonate and the like can be mentioned.

Examples of the pyrogallol trisulfonate type photoacid generator include all of the hydroxyl groups of pyrogallol, phloroglysin, catechol, resorcinol, and hydroquinone, trifluoromethanesulfonate, nonafluorobutanesulfonate, heptadecafluorooctanesulfonate, 2,2,2 -Trifluoroethane sulfonate, pentafluorobenzene sulfonate, 4-trifluoromethylbenzene sulfonate, 4-fluorobenzene sulfonate, toluene sulfonate, benzene sulfonate, naphthalene sulfonate, camphor sulfonate, octane sulfonate, dodecylbenzene sulfonate, butane sulfonate, methane sulfonate, etc. Embedded image

Examples of the nitrobenzylsulfonate type photoacid generator include 2,4-dinitrobenzylsulfonate,
-Nitrobenzylsulfonate, 2,6-dinitrobenzylsulfonate, and as the sulfonate,
Specifically, trifluoromethanesulfonate, nonafluorobutanesulfonate, heptadecafluorooctanesulfonate, 2,2,2-trifluoroethanesulfonate, pentafluorobenzenesulfonate, 4-trifluoromethylbenzenesulfonate, 4-fluorobenzenesulfonate, toluenesulfonate Benzenesulfonate, naphthalenesulfonate, camphorsulfonate, octanesulfonate, dodecylbenzenesulfonate, butanesulfonate, methanesulfonate and the like. A compound in which the nitro group on the benzyl side is replaced with a trifluoromethyl group can also be used in the same manner.

Examples of the sulfone-type photoacid generator include bis (phenylsulfonyl) methane, bis (4-methylphenylsulfonyl) methane, bis (2-naphthylsulfonyl) methane, and 2,2-bis (phenylsulfonyl) propane. , 2,2-bis (4-methylphenylsulfonyl)
Propane, 2,2-bis (2-naphthylsulfonyl) propane, 2-methyl-2- (p-toluenesulfonyl)
Propiophenone, 2- (cyclohexylcarbonyl)
-2- (p-toluenesulfonyl) propane, 2,4-
Dimethyl-2- (p-toluenesulfonyl) pentane-
3-one and the like.

Examples of the glyoxime derivative type photoacid generator include bis-o- (p-toluenesulfonyl) -α-
Dimethylglyoxime, bis-o- (p-toluenesulfonyl) -α-diphenylglyoxime, bis-o-
(P-toluenesulfonyl) -α-dicyclohexylglyoxime, bis-o- (p-toluenesulfonyl)-
2,3-pentanedione glyoxime, bis-o- (p
-Toluenesulfonyl) -2-methyl-3,4-pentanedione glyoxime, bis-o- (n-butanesulfonyl) -α-dimethylglyoxime, bis-o- (n-
Butanesulfonyl) -α-diphenylglyoxime, bis-o- (n-butanesulfonyl) -α-dicyclohexylglyoxime, bis-o- (n-butanesulfonyl) -2,3-pentanedione glyoxime, bis-o
-(N-butanesulfonyl) -2-methyl-3,4-pentanedione glyoxime, bis-o- (methanesulfonyl) -α-dimethylglyoxime, bis-o- (trifluoromethanesulfonyl) -α-dimethylglyme Oxime, bis-o- (1,1,1-trifluoroethanesulfonyl) -α-dimethylglyoxime, bis-o- (t
ert-butanesulfonyl) -α-dimethylglyoxime, bis-o- (perfluorooctanesulfonyl)-
α-dimethylglyoxime, bis-o- (cyclohexylsulfonyl) -α-dimethylglyoxime, bis-o
-(Benzenesulfonyl) -α-dimethylglyoxime, bis-o- (p-fluorobenzenesulfonyl)-
α-dimethylglyoxime, bis-o- (p-tert
-Butylbenzenesulfonyl) -α-dimethylglyoxime, bis-o- (xylenesulfonyl) -α-dimethylglyoxime, bis-o- (camphorsulfonyl)
-Α-dimethylglyoxime and the like.

Among the photoacid generators that are preferably used, sulfonium salts, bissulfonyldiazomethane,
N-sulfonyloxyimide.

Although the optimum anion of the generated acid varies depending on the easiness of cleavage of the acid labile group used in the polymer, etc., those having no volatility and those having extremely low diffusivity are generally selected. In this case, suitable anions are benzenesulfonic acid anion, toluenesulfonic acid anion, and 4- (4
-Toluenesulfonyloxy) benzenesulfonic acid anion, pentafluorobenzenesulfonic acid anion,
2,2,2-trifluoroethanesulfonic acid anion,
Nonafluorobutanesulfonic acid anion, heptadecafluorooctanesulfonic acid anion and camphorsulfonic acid anion.

The amount of the photoacid generator (C) to be added in the chemically amplified positive resist composition of the present invention is 0 to 20 parts by weight, preferably 1 to 10 parts by weight, per 100 parts by weight of the solids in the resist composition. Department. The photoacid generators (C) can be used alone or in combination of two or more. Furthermore, a photoacid generator having a low transmittance at the exposure wavelength can be used, and the transmittance in the resist film can be controlled by the amount of addition.

As the dissolution controlling agent of the component (D), a compound having a weight-average molecular weight of 100 to 1,000 and having two or more phenolic hydroxyl groups in the molecule can be obtained by acid-labile the hydrogen atom of the phenolic hydroxyl group. Average 1 overall
Compounds substituted at a rate of 0 to 100 mol% are preferred.
The compound has a weight average molecular weight of 100 to 1,000.
0, preferably 150 to 800. The compounding amount of the dissolution controlling agent is 0 to 50 parts by weight, preferably 5 to 50 parts by weight, more preferably 10 to 50 parts by weight based on 100 parts by weight of the base resin.
30 parts by weight, and can be used alone or in combination of two or more. If the amount is too small, the resolution may not be improved. If the amount is too large, the film thickness of the pattern is reduced, and the resolution tends to decrease.

Examples of the dissolution controlling agent of the component (D) preferably used include bis (4- (2'-tetrahydropyranyloxy) phenyl) methane and bis (4-
(2′-tetrahydrofuranyloxy) phenyl) methane, bis (4-tert-butoxyphenyl) methane,
Bis (4-tert-butoxycarbonyloxyphenyl) methane, bis (4-tert-butoxycarbonylmethyloxyphenyl) methane, bis (4- (1′-ethoxyethoxy) phenyl) methane, bis (4- (1 ′)
-Ethoxypropyloxy) phenyl) methane, 2,2
-Bis (4 '-(2 "-tetrahydropyranyloxy)) propane, 2,2-bis (4'-(2" -tetrahydrofuranyloxy) phenyl) propane, 2,2
-Bis (4'-tert-butoxyphenyl) propane, 2,2-bis (4'-tert-butoxycarbonyloxyphenyl) propane, 2,2-bis (4-te
rt-butoxycarbonylmethyloxyphenyl) propane, 2,2-bis (4 ′-(1 ″ -ethoxyethoxy) phenyl) propane, 2,2-bis (4′-
(1 ″ -ethoxypropyloxy) phenyl) propane, 4,4-bis (4 ′-(2 ″ -tetrahydropyranyloxy) phenyl) tertbutyl valerate, 4,4
Tert-butyl bis (4 ′-(2 ″ -tetrahydrofuranyloxy) phenyl) valerate, tert-butyl 4,4-bis (4′-tert-butoxyphenyl) valerate
Butyl, tert-butyl 4,4-bis (4-tert-butoxycarbonyloxyphenyl) valerate, 4,4-
Tertbutyl bis (4'-tert-butoxycarbonylmethyloxyphenyl) valerate, tertbutyl 4,4-bis (4 '-(1 "-ethoxyethoxy) phenyl) valerate, 4,4-bis (4' -(1 ″ -ethoxypropyloxy) phenyl) tertbutyl valerate, tris (4- (2′-tetrahydropyranyloxy) phenyl) methane, tris (4- (2′-tetrahydrofuranyloxy) phenyl) methane, Tris (4-
tert-butoxyphenyl) methane, tris (4-t
tert-butoxycarbonyloxyphenyl) methane,
Tris (4-tert-butoxycarbonyloxymethylphenyl) methane, tris (4- (1′-ethoxyethoxy) phenyl) methane, tris (4- (1′-ethoxypropyloxy) phenyl) methane, 1,1,2 −
Tris (4 ′-(2 ″ -tetrahydropyranyloxy) phenyl) ethane, 1,1,2-tris (4′-
(2 ″ -tetrahydrofuranyloxy) phenyl) ethane, 1,1,2-tris (4′-tert-butoxyphenyl) ethane, 1,1,2-tris (4′-ter
(t-butoxycarbonyloxyphenyl) ethane, 1,
1,2-tris (4′-tert-butoxycarbonylmethyloxyphenyl) ethane, 1,1,2-tris (4 ′-(1′-ethoxyethoxy) phenyl) ethane, 1,1,2-tris (4 '-(1'-ethoxypropyloxy) phenyl) ethane and the like.

As the basic compound (E), a compound capable of suppressing the rate of diffusion of the acid generated from the photoacid generator into the resist film is suitable. The composition improves the resolution by suppressing the diffusion rate of acid in the resist film, suppresses the change in sensitivity after exposure, reduces the dependence on the substrate and environment, and improves the exposure margin and pattern profile. can do.

Examples of the basic compound (E) include primary, secondary, and tertiary aliphatic amines, hybrid amines, aromatic amines, heterocyclic amines, and carboxy groups. Embedded image, a nitrogen-containing compound having a sulfonyl group, a nitrogen-containing compound having a hydroxy group, a nitrogen-containing compound having a hydroxyphenyl group, an alcoholic nitrogen-containing compound, an amide derivative, and an imide derivative.

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

Examples of the mixed amines include dimethylethylamine, methylethylpropylamine, benzylamine, phenethylamine and benzyldimethylamine. Specific examples of aromatic amines and heterocyclic amines include aniline derivatives (for example, aniline, N-methylaniline, N-ethylaniline, N-propylaniline, N, N-dimethylaniline, 2-methylaniline, -Methylaniline, 4-methylaniline, ethylaniline, propylaniline, trimethylaniline, 2-nitroaniline, 3-nitroaniline,
-Nitroaniline, 2,4-dinitroaniline, 2,6
-Dinitroaniline, 3,5-dinitroaniline, N,
N-dimethyltoluidine, etc.), diphenyl (p-tolyl) amine, methyl diphenylamine, triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, pyrrole derivatives (for example, pyrrole, 2H
-Pyrrole, 1-methylpyrrole, 2,4-dimethylpyrrole, 2,5-dimethylpyrrole, N-methylpyrrole and the like), oxazole derivatives (for example, oxazole,
Isoxazole, etc.), thiazole derivatives (eg, thiazole, isothiazole, etc.), imidazole derivatives (eg, imidazole, 4-methylimidazole,
-Methyl-2-phenylimidazole, etc.), pyrazole derivatives, furazane derivatives, pyrroline derivatives (e.g., pyrroline, 2-methyl-1-pyrroline, etc.), pyrrolidine derivatives (e.g., pyrrolidine, N-methylpyrrolidine, pyrrolidinone, N-methyl) Pyrrolidone, etc.), imidazoline derivatives, imidazolidine derivatives, pyridine derivatives (for example, pyridine, methylpyridine, ethylpyridine, propylpyridine, butylpyridine, 4- (1-butylpentyl) pyridine, dimethylpyridine, trimethylpyridine, triethylpyridine, phenyl Pyridine, 3-methyl-2-phenylpyridine, 4-tert-butylpyridine, diphenylpyridine, benzylpyridine, methoxypyridine, butoxypyridine, dimethoxypyridine,
1-methyl-2-pyridine, 4-pyrrolidinopyridine,
1-methyl-4-phenylpyridine, 2- (1-ethylpropyl) pyridine, aminopyridine, dimethylaminopyridine, etc.), pyridazine derivatives, pyrimidine derivatives,
Pyrazine derivatives, pyrazoline derivatives, pyrazolidine derivatives, piperidine derivatives, piperazine derivatives, morpholine derivatives, indole derivatives, isoindole derivatives, 1
H-indazole derivative, indoline derivative, quinoline derivative (for example, quinoline, 3-quinolinecarbonitrile, etc.), isoquinoline derivative, cinnoline derivative, quinazoline derivative, quinoxaline derivative, phthalazine derivative, purine derivative, pteridine derivative, carbazole derivative, 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 are exemplified.

Examples of the nitrogen-containing compound having a carboxyl group include, for example, aminobenzoic acid, indolecarboxylic acid, amino acid derivatives (for example, nicotinic acid, alanine, arginine, aspartic acid, glutamic acid, glycine, histidine, isoleucine, glycyl Leucine,
Leucine, methionine, phenylalanine, threonine, lysine, 3-aminopyrazine-2-carboxylic acid, methoxyalanine, etc.). Examples of the nitrogen-containing compound having a sulfonyl group include 3-pyridinesulfonic acid,
-Pyridinium toluenesulfonate and the like are exemplified, nitrogen-containing compounds having a hydroxy group, nitrogen-containing compounds having a hydroxyphenyl group, and alcoholic nitrogen-containing compounds include 2-hydroxypyridine, aminocresol,
2,4-quinolinediol, 3-indolemethanol hydrate, monoethanolamine, diethanolamine, triethanolamine, N-ethyldiethanolamine, N, N-diethylethanolamine, triisopropanolamine, 2,2′-iminodiethanol,
-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. Amide derivatives 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.

Further, part or all of the hydrogen atoms of the hydroxyl group of the nitrogen-containing compound having a hydroxyl group were replaced with a methyl group, an ethyl group, a methoxymethyl group, a methoxyethoxymethyl group, an acetyl group, an ethoxyethyl group, or the like. Compounds are exemplified, and methyl-substituted, acetyl-substituted, methoxymethyl-substituted, and methoxyethoxymethyl-substituted ethanolamine, diethanolamine, and triethanolamine are preferably used. Specifically, tris (2-methoxyethyl) amine, tris (2-ethoxyethyl) amine, tris (2-acetoxyethyl) amine, tris {2- (methoxymethoxy) ethyl} amine, and tris {2- (methoxyethoxy) amine ) Ethyl} amine, tris [2-{(2-methoxyethoxy) methoxy} ethyl] amine, tris {2- (2-methoxyethoxy) ethyl} amine, tris {2- (1-methoxyethoxy) ethyl} amine, Tris {2- (1-ethoxyethoxy) ethyl} amine, tris {2- (1-ethoxypropoxy) ethyl} amine, tris [2-{(2-
Hydroxyethoxy) ethoxy [ethyl] amine.

The basic compound can be used alone or in combination of two or more. The compounding amount is 0 to 100 parts by weight of the solid content in the resist material.
A mixture of 2 parts by weight, particularly 0.01 to 1 part by weight, is suitable. If the amount exceeds 2 parts by weight, the sensitivity may be too low.

The chemically amplified positive resist composition of the present invention may further contain a surfactant for improving coating properties.

Examples of the surfactant include, but are not particularly limited to, polyoxyethylene alkyl such as polyoxyethylene lauryl ether, polyoxyethylene steryl ether, polyoxyethylene cetyl ether, and polyoxyethylene olein ether. Ethers, polyoxyethylene octyl phenol ether,
Polyoxyethylene alkyl allyl ethers such as polyoxyethylene nonylphenol ether, polyoxyethylene polyoxypropylene block copolymers,
Sorbitan monolaurate, sorbitan monopalmitate, sorbitan fatty acid esters such as sorbitan monostearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate,
Nonionic surfactants of polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan trioleate and polyoxyethylene sorbitan tristearate; EFTOP EF301, EF303, EF35
2 (Tochem Products), Mega Fuck F171, F
172, F173 (Dainippon Ink and Chemicals), Florado FC430, FC431 (Sumitomo 3M), Asahigard AG710, Surflon S-381, S-38
2, SC101, SC102, SC103, SC10
4, SC105, SC106, Surfynol E100
4, KH-10, KH-20, KH-30, KH-40
(Asahi Glass) and other fluorochemical surfactants, organosiloxane polymers KP341, X-70-092, X-70-
093 (Shin-Etsu Chemical Co., Ltd.), acrylic acid-based or methacrylic acid-based polyflow No. 75, no. 95 (Kyoeisha Yushi Kagaku Kogyo), among which FC430, Surflon S
-381, Surfynol E1004, KH-20, K
H-30 is preferred. These can be used alone or in combination of two or more.

The amount of the surfactant to be added to the chemically amplified positive resist composition of the present invention is 2 parts by weight or less, preferably 1 part by weight or less based on 100 parts by weight of the solids in the resist composition. .

A chemically amplified positive resist material containing (A) the organic solvent of the present invention, (B) a mixture of the high molecular compounds represented by the above general formulas (1) and (2), and (C) an acid generator. When is used for manufacturing various integrated circuits, a known lithography technique can be used without particular limitation.

A substrate (Si, SiO ₂ ,
SiN, SiON, TiN, WSi, BPSG, SO
G, organic antireflection film, etc.), spin coating, roll coating, flow coating, dip coating, spray coating,
It is applied by an appropriate application method such as doctor coating so that the applied film thickness is 0.1 to 2.0 μm, and is applied on a hot plate at 60 to 150 ° C. for 1 to 10 minutes, preferably 80 to
Pre-bake at ~ 120 ° C for 1-5 minutes. Next, ultraviolet light, far ultraviolet light, electron beam, X-ray, excimer laser, γ
A desired pattern is exposed through a predetermined mask at a light source selected from radiation, synchrotron radiation and the like, preferably at an exposure wavelength of 300 nm or less. Exposure is 1-20
About 0 mJ / cm ² , preferably 10 to 100 mJ / c
Exposure is preferably performed so as to be about m ² . Post exposure bake (PEB) on a hot plate at 60 to 150 ° C. for 1 to 5 minutes, preferably 80 to 120 ° C. for 1 to 3 minutes.

Further, 0.1-5%, preferably 2-3%
Using a developer of an aqueous alkali solution such as tetramethylammonium hydroxide (TMAH) for 0.1 to 3 minutes, preferably 0.5 to 2 minutes, a dipping method, a puddle method, and a spray method. A target pattern is formed on the substrate by developing by a conventional method such as a method. In addition, the resist material of the present invention is particularly suitable for the use of far ultraviolet rays of 254 to 193 nm,
It is most suitable for fine patterning with 57 nm vacuum ultraviolet ray, electron beam, X-ray, excimer laser, γ-ray and synchrotron radiation. In addition, when the above range is out of the upper limit and the lower limit, a desired pattern may not be obtained.

[0078]

EXAMPLES The present invention will be described below in detail with reference to examples and comparative examples, but the present invention is not limited to the following examples. [Examples and Comparative Examples] Chemically amplified positive resist materials shown in Tables 1 and 2 were prepared. The components of the resist composition shown in Tables 1 and 2 are as follows. Polymer A: the hydroxyl group of poly p-hydroxystyrene is 1-
Weight average molecular weight 1 protected by 15 mol% of ethoxyethyl group and 15 mol% of tert-butoxycarbonyl group.
2,000 polymers. Polymer B: the hydroxyl group of poly p-hydroxystyrene is 1-
A polymer having a weight average molecular weight of 13,000, crosslinked with 25 mol% of ethoxyethyl groups and further 3 mol% with 1,4-butanediol divinyl ether. Polymer C: the hydroxyl group of poly p-hydroxystyrene is 1-
A polymer having a weight average molecular weight of 12,000 protected with 30 mol% of ethoxyethyl groups. Polymer D: a copolymer of p-hydroxystyrene and 1-ethylcyclopentyl methacrylate having a composition ratio (molar ratio) of 72:28 and a p-hydroxystyrene portion of 1,4-butanediol divinyl ether of 2 mol % Crosslinked polymer having a weight average molecular weight of 11,000. Polymer E: a copolymer of p-hydroxystyrene, 1-ethylcyclopentyl methacrylate, and isobornyl acrylate having a composition ratio (molar ratio) of 73:22:
5, and a polymer having a weight average molecular weight of 16,000. Polymer F: a copolymer of p-hydroxystyrene, 1-ethylcyclopentyl methacrylate, and 1-tetrahydrofuranylmethyl methacrylate having a composition ratio (molar ratio) of 68: 27: 5 and a weight average molecular weight of 1
6,000 polymers. PAG1: triphenylsulfonium 4- (4'-methylphenylsulfonyloxy) phenylsulfonate PAG2: (4-tert-butylphenyl) diphenylsulfonium 4- (4'-methylphenylsulfonyloxy) phenylsulfonate PAG3: bis (cyclohexyl) Sulfonyl) diazomethane PAG4: Bis (2,4-dimethylphenylsulfonyl) diazomethane Dissolution controlling agent A: Bis (4- (2′-tetrahydropyranyloxy) phenyl) methane Basic compound A: Tris (2-methoxyethyl) amine Surfactant A: FC-430 (Sumitomo 3M) Surfactant B: Surflon S-381 (Asahi Glass) Solvent A: Propylene glycol methyl ether acetate Solvent B: Ethyl lactate

[0079]

[Table 1]

[0080]

[Table 2]

After the obtained resist material was filtered through a 0.2 μm Teflon (registered trademark) filter, the resist solution was spin-coated on a silicone wafer and applied to 0.6 μm.

Next, this silicone wafer was put into 100
Bake for 90 seconds on a hot plate at 90 ° C. Furthermore, an excimer laser stepper (Nikon Corporation, NSR2005
Exposure is performed using EXNA = 0.5, and baked at 110 ° C. for 90 seconds (PEB: post exposure ba).
After performing ke) and developing with an aqueous solution of 2.38% tetramethylammonium hydroxide, positive patterns (Examples 1 to 4 and Comparative Examples 1 to 5) could be obtained.

The obtained resist pattern was evaluated as follows. Resist pattern evaluation method: The exposure amount that resolves the top and bottom of a 0.24 μm line and space at 1: 1 is defined as the optimal exposure amount (sensitivity: Eop), and the minimum of the separated line and space at this exposure amount The line width was taken as the resolution of the evaluation resist. For the shape of the resolved resist pattern, the cross section of the resist was observed using a scanning electron microscope. In addition, the PED stability of the resist was determined as follows: after exposure at the optimal exposure dose, after standing for 24 hours, PEB (post
Exposure bake) was performed, and the evaluation was made based on the fluctuation value of the line width. The smaller the fluctuation value, the higher the PED stability.

Table 3 shows the results of the resist pattern evaluation. Evaluation method other than pattern evaluation: Regarding the decrease in film thickness after development of the resist material, the cross section of the resist in the unexposed area was observed and measured using a scanning electron microscope, and the coating film thickness before development (0.6 μm) was reduced. On the other hand, when the decrease in film thickness was within 0.5% (within 0.003 μm), it was expressed as good, when it was within 1%, slightly bad, and when it was more than that, it was expressed as bad. Further, with respect to the dry etching resistance after development, the resist was actually etched, and the pattern shape after that was observed by observing the cross section of the resist using a scanning electron microscope. The etching was performed under the following conditions.

[0085]

[Table 3]

[0086]

As described above, the chemically amplified resist composition of the present invention comprises a polyhydroxystyrene derivative and a copolymer of hydroxystyrene and (meth) acrylic acid ester, in particular, a ternary copolymer. Chemically amplified positive type with improved dry etching resistance, high sensitivity and high resolution, process adaptability, and improved reduction of pattern film thickness after development with alkaline aqueous solution. It is possible to provide a resist material.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Kazuhiro Hirahara 28-1 Nishifukushima, Nishi-Jukumura, Nakakushijo-gun, Niigata Prefecture Within Synthetic Research Laboratory, Shin-Etsu Chemical Co., Ltd. 28-1 Oishi Nishifukushima Shin-Etsu Chemical Co., Ltd., Synthetic Technology Laboratory (72) Inventor Wataru Kusaki 28-1 Nishifukushima, Niigata Pref. Akihiro 28-1 Nishifukushima, Nishifukushima, Nakakubijo-gun, Niigata Prefecture Inside Synthetic Technology Research Laboratory, Shin-Etsu Chemical Co., Ltd.

Claims (4)

[Claims] 1. A repeating unit represented by the following general formula (1)
Having a weight average molecular weight of 1,000 to 500,000
0 and a polymer represented by the following general formula (2)
Weight average molecular weight having a repeating unit of 1,000 to 5
A polymer mixture with a polymer compound of
A chemically amplified resist material comprising: Embedded image(Wherein R is a hydroxyl group or OR^ThreeA group represented by R¹Is a hydrogen atom
Or a methyl group; ^TwoIs a straight chain having 1 to 8 carbon atoms,
A branched or cyclic alkyl group;^Three, R^FourIs acid labile
A group represented by R^FiveRepresents a methyl group or an ethyl group. Z is charcoal
A linear, branched or cyclic alkylene group having a prime number of 1 to 10
Is shown. X is 0 or a positive integer, and y is a positive integer.
Is a number satisfying x + y ≦ 5, and m is 0 or a positive integer.
Is a number, n is a positive integer and satisfies m + n ≦ 5
Is a number. p, q, r, and s are 0 or a positive number, and p + q
It is a number that satisfies + r + s = 1. )(Where R⁶, R⁷, R⁸Represents a hydrogen atom or a methyl group
Then R⁹Represents a methyl group or an ethyl group. E is carbon number 1
Represents 10 to 10 linear, branched or cyclic alkylene groups
You. R^TenIs linear, branched or cyclic having 1 to 20 carbon atoms
Alkyl group or carbon containing oxygen or sulfur atom
Represents a linear, branched or cyclic alkyl group of Formulas 1 to 20
You. R¹¹Represents a tertiary alkyl group having 1 to 20 carbon atoms. k
Is 0 or a positive integer, and is a number satisfying k ≦ 5.
t and w are positive numbers, and u and v are 0 or positive numbers,
One of u and v is not 0, and t + u + v + w =
It is a number that satisfies 1. ) 2. A chemically amplified positive resist material comprising (A) an organic solvent, (B) a polymer mixture according to claim 1 as a base resin, and (C) an acid generator. 3. A chemically amplified positive type comprising (A) an organic solvent, (B) a polymer mixture according to claim 1 as a base resin, (C) an acid generator, and (D) a dissolution controlling agent. Resist material. 4. The chemically amplified positive resist composition according to claim 2, further comprising (E) a basic compound as an additive.