JP3528429B2 - Chemically amplified positive resist material - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention has a high sensitivity to high-energy rays such as deep ultraviolet rays, electron beams, and X-rays, and is suitable for a fine processing technique capable of forming a pattern by developing with an alkaline aqueous solution. Amplified positive resist material.

[0002]

2. Description of the Related Art LSI to be Solved
Due to the higher integration and higher speed, fine patterning of pattern rules is required, and far-ultraviolet lithography is expected as a next-generation fine processing technology. The deep-UV lithography can also process 0.3 to 0.4 μm, and when a resist material having low light absorption is used, it becomes possible to form a pattern having a side wall that is almost vertical to the substrate.

In recent years, a technique using a high-intensity KrF excimer laser as a light source for far-ultraviolet rays has been attracting attention. In order to use this as a mass production technique, a resist material having low light absorption and high sensitivity is demanded. Has been done.

From such a viewpoint, a chemically amplified positive resist material using an acid catalyst developed in recent years (Japanese Patent Publication No. 2-2
7660, JP-A-63-27829, etc.)
Has excellent sensitivity, resolution, and dry etching resistance, and is a particularly promising resist material for deep ultraviolet lithography.

However, one of the drawbacks of the chemically amplified positive resist material is that from exposure to PEB (Post Expo).
The problem that the line pattern becomes T-top shape when the pattern is formed, that is, the upper part of the pattern becomes thicker if the leaving time until the "Sure Bake" is long (PED
(Post Exposure Delay)), or a basic substrate, in particular, a silicon nitride or titanium nitride substrate, has a problem that a pattern around the substrate becomes thicker, that is, a so-called bottoming phenomenon occurs. The T-top phenomenon is considered to be because the solubility of the resist film surface is lowered, and the tailing on the substrate surface is considered to be because the solubility is lowered near the substrate. Further, there is a problem that a dark reaction of elimination of an acid labile group progresses between exposure and PEB (PED), and a remaining dimension of a line becomes small. These are major drawbacks when the chemically amplified positive resist material is put to practical use.

Further, due to this drawback, the conventional chemically amplified positive type resist material has a problem that it is difficult to control the dimensions in the lithography process and the dimension control is impaired even when the substrate is processed by dry etching [W. Hins
berg, et. al. J. Photopolym.
Sci. Tecnol. , 6 (4), 535-546
(1993), T.S. Kumada, et. al. J.
Photopolym. Sci. Tecnol. , 6
(4), 571-574 (1993)].

In the chemically amplified positive resist material, P
It is considered that the cause of the T-top shape or the bottoming of the substrate surface due to ED is largely related to the basic compound in the air or the substrate surface. The acid generated on the surface of the resist film by exposure reacts with the basic compound in the air to be inactivated, and the longer the standing time until PED, the more the amount of inactivated acid increases. Decomposition is less likely to occur. Therefore, an insoluble layer is formed on the surface, and the pattern has a T-top shape.

Therefore, by adding a basic compound, the influence of the basic compound in the air can be suppressed.
It is well known that ED is also effective, and various proposals have been made (Japanese Patent Laid-Open Nos. 5-158239 and 5-232).
No. 706, No. 5-249662, No. 5-249683
No. 5, No. 5-257282, No. 5-289322, No. 5-289340, No. 6-194834, No. 6-2.
42605, 6-242606, 6-2637.
No. 16, No. 6-263717, No. 6-266110.
No. 6, No. 6-266111, No. 7-128859, No. 7-92678, No. 7-92680, No. 7-926.
No. 81, No. 7-120929, No. 7-134419).

All of these nitrogen-containing compounds have an acid dissociation constant pKa in the range of 2 to 6 and a tert-butoxycarbonyl group or tert-butoxycarbonyl group having a high activation energy for elimination reaction.
By combining with an alkali-soluble resin substituted with a butyl ester group or the like, it is effective in reducing the T-top shape in PED.

However, the above-mentioned nitrogen-containing compound has a small effect on the trailing of the substrate, the sensitivity and the resolution are lowered by the addition of the basic substance, and when the basic substance having a pKa of 6 or more is added. Had the drawback that the sensitivity and resolution were significantly reduced. Thus, the basic compound alone can alleviate the problem of the T-top shape, but cannot improve the bottoming of the substrate.

In order to improve the trailing of the substrate, it is most effective to make the substituent of the alkali-soluble resin into an acid labile group having a low activation energy for the elimination reaction and a high reactivity. However, when a highly reactive substituent is used, the reaction control, especially the dark reaction in PED, progresses in the unexposed portion, and the line size is reduced (slimming) in PED.
There was a problem of causing film loss on the line surface, and this method was hardly a satisfactory solution.

The present invention has been made in view of the above circumstances, and has a high sensitivity and a high resolution to high energy rays such as deep ultraviolet rays, electron beams, and X-rays, and pattern formation by developing with an alkaline aqueous solution. It is an object of the present invention to provide a chemically amplified positive resist material suitable for possible fine processing technology.

[0013]

Means for Solving the Problems and Modes for Carrying Out the Invention As a result of extensive studies conducted by the present inventor in order to achieve the above object, a chemistry containing an organic solvent, a base resin, an acid generator, a dissolution inhibitor, etc. A compound compound represented by the following general formula (1) or (2) and having a weight average molecular weight of 1,000 to 1,000,000 as a basic compound is added to the amplified positive resist composition, and By blending a polymer compound composed of a repeating unit represented by the following general formula (3) as a base resin and having a weight average molecular weight of 1,000 to 100,000, the above-mentioned substrate tailing and line size reduction can be achieved. , A chemical amplification positive type resist that solves problems such as film loss, has high sensitivity and resolution, is highly practical, is advantageous for precision microfabrication, and provides a very effective resist material for VLSI etc. It was found that the door material is obtained.

[0014]

[Chemical 3] (However, in the formula, R ¹ and R ³ are each independently a hydrogen atom or a linear alkyl group having 1 to 10 carbon atoms, and R ² is 1 carbon atom.
10 is a linear or branched alkylene group, and a is 0 or 1. Further, p and q are 0.2 ≦ p / p + q ≦
It is a number that satisfies 1, and p + q and r are numbers that satisfy the above weight average molecular weight. )

[0015]

[Chemical 4] (However, in the formula, R ⁴ is a hydrogen atom or a linear alkyl group having 1 to 10 carbon atoms, R ⁵ is a hydrogen atom or an acid labile group, and at least one is an acid labile group, m and n are
The hydrogen atom of the phenolic hydroxyl group in the molecule is a number satisfying the value in which the average of the hydrogen atoms of the phenolic hydroxyl group is substituted by the acid labile group as a whole at an average of 10 to 100 mol%, and b is 1, 2 or 3. )

That is, as a result of various studies on the above-mentioned conventional techniques, the present inventor controls the reaction by adding a weakly basic compound when a highly reactive substituent is used as the substituent of the alkali-soluble resin. However, the addition of the polymer type amino acrylate compound of the above formula (1) or (2), which is a strongly basic compound as a basic compound, cannot improve the film loss and prevent the dark reaction. Further, as an alkali-soluble resin, a polymer compound comprising a repeating unit of the above formula (3) and having a highly reactive substituent (acid labile group) such as an acetal group, an alkoxy group or an alkylsiloxy group is added and used in combination. By doing so, it is possible to increase the uniformity in the film and improve the verticality of the resolved pattern profile. Therefore, the T-top shape in PED and the pattern due to dark reaction can be achieved. Eliminate thinned eliminate footing under basic substrate, in which further found that very practical high chemically amplified positive resist materials improved the resolving power can be obtained, leading to completion of the present invention.

Therefore, the present invention comprises (1) a polymer compound represented by the general formula (1) or (2) and having a weight average molecular weight of 1,000 to 1,000,000. A chemically amplified positive resist composition (2) (A) comprising an organic solvent (B) as a base resin, comprising a repeating unit represented by the above general formula (3), and having a weight average molecular weight of 1,000 to 1.
Polymer compound (C) acid generator (D) having a molecular weight of 100,000 as a dissolution controller of the polymer compound (E) of the formula (1) or (2), which is 0,000.
And a compound having two or more phenolic hydroxyl groups in the molecule, in which the hydrogen atom of the phenolic hydroxyl group is replaced by an acid labile group at a rate of more than 0 mol% and not more than 100 mol% on average as a whole. Chemically amplified positive type resist material (3) (A) Organic solvent (B) as base resin, polymer compound (C) acid generator (D) above formula (1) Alternatively, the polymer compound (F) as a dissolution control agent of (2) has a weight average molecular weight of more than 1,000 and 3,000 or less, and the hydrogen atom of the phenolic hydroxyl group of the compound having a phenolic hydroxyl group in the molecule is acid. The average is over 0 mol% and 100 as a whole due to unstable groups.
A chemically amplified positive resist material (4) characterized by containing a compound partially substituted at a ratio of not more than mol% (4) (A) an organic solvent (B) as a base resin, the polymer compound of the above formula (3) ( C) Acid generator (D) Polymer compound of formula (1) or (2) (E) As a dissolution control agent, the molecular weight is 100 to 1,000.
A compound (F) in which the hydrogen atom of the phenolic hydroxyl group of the compound having two or more phenolic hydroxyl groups in the molecule is replaced with an acid labile group at a rate of more than 0 mol% and less than 100 mol% on average Another dissolution control agent having a weight average molecular weight of 100
The number of hydrogen atoms of the phenolic hydroxyl group of the compound having a phenolic hydroxyl group in the molecule of more than 0 and 3,000 or less exceeds 0 mol% on average as a whole due to the acid labile group and 1
Provided is a chemically amplified positive resist material containing a compound partially substituted in an amount of not more than 00 mol%.

The present invention will be described in more detail below. The chemically amplified positive resist composition of the present invention is characterized by containing a polymer compound represented by the following general formula (1) or (2). To do.

[0019]

[Chemical 5] (However, in the formula, R ¹ and R ³ are each independently a hydrogen atom or a linear alkyl group having 1 to 10 carbon atoms, and R ² is 1 carbon atom.
10 is a linear or branched alkylene group, and a is 0 or 1. Further, p and q are 0.2 ≦ p / p + q ≦
It is a number that satisfies 1, and p + q and r are numbers that satisfy the above weight average molecular weight. )

In the above formula (1), R ¹ and R ³ are, for example, hydrogen atom, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, tert- Examples thereof include a butyl group. Examples of R ² include methylene group, ethylene group, propylene group,
Butylene group and the like can be mentioned. a is 0 or 1. In this case, when a = 0 and in the case of the formula (2), a quaternary ammonium salt which becomes N ⁺ and OH ⁻ is shown. Also, p and q are 0.2
≦ p / p + q ≦ 1, preferably 0.3 ≦ p / p + q ≦
It is a number that satisfies 0.8. p + q and r are numbers which satisfy the following weight average molecular weights.

The polymer compound of the above formula (1) has a weight average molecular weight of 1,000 to 1,000,000, preferably 10,000 to 500,000. It causes a relation.

The blending amount of the polymer compound of the above formula (1) is
0.0 for 100 parts of acid generator (parts by weight, the same applies below)
It is 1 to 1,000 parts, preferably 0.1 to 100 parts.

The chemically amplified positive resist material of the present invention is
Preparation as a chemically amplified positive resist material containing a polymer compound of the above formula (1) or (2) as a basic substance and containing an organic solvent, a base resin, an acid generator, a dissolution controller, etc. Is preferred.

The organic solvent (A) used in the present invention may be any organic solvent in which the acid generator, the base resin, the dissolution control agent, etc. can be dissolved. Examples of such an organic solvent include ketones such as cyclohexanone and methyl-2-n-amyl ketone, 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-
Alcohols such as methoxy-2-propanol and 1-ethoxy-2-propanol, 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 and the like. These can be used alone or in combination of two or more, but are not limited thereto. In the present invention, among these organic solvents, diethylene glycol dimethyl ether and 1-ethoxy-2, which have the best solubility of the acid generator in the resist component, are used.
-Propanol is preferably used.

The amount of the organic solvent used is preferably 200 to 1,000 parts, more preferably 250 to 800 parts, relative to 100 parts of the base resin. If it is less than 200 parts, the compatibility decreases,
In some cases, the film formability is inferior, and when it exceeds 1,000 parts, it becomes a thin film when the resist film is formed, and there is a case that it cannot be used.

Next, as the base resin of the second invention of the present invention, a polymer compound comprising a repeating unit represented by the following general formula (3) and having a weight average molecular weight of 1,000 to 100,000 is suitable. Is.

[0027]

[Chemical 6] (However, in the formula, R ⁴ is a hydrogen atom or a linear alkyl group having 1 to 10 carbon atoms, R ⁵ is a hydrogen atom or an acid labile group, but at least one is an acid labile group, m , N is a number satisfying a value such that the hydrogen atom of the phenolic hydroxyl group in the molecule is substituted by the acid labile group at an average ratio of more than 0 mol% and not more than 100 mol%, and b is 1 , 2 or 3.)

In the above formula (3), R ⁴ may be the same group as the above R ¹ . Here, in the formula (3), various kinds of acid labile groups are selected, but in particular, a group represented by the following formula (4), a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, It is preferably a tetrahydropyranyl group, a tetrahydrofuranyl group or a trialkylsilyl group.

[0029]

[Chemical 7] (However, in the formula, R ⁶ and R ⁷ are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms,
R ⁸ is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms. )

Examples of the linear or branched alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an iso-butyl group and a tert-butyl group, and a cyclic alkyl group. A cyclohexyl group etc. can be illustrated as an alkyl group.

Specific examples of the acid labile group represented by the above formula (4) include methoxyethyl group, ethoxyethyl group and n.
-Propoxyethyl group, iso-propoxyethyl group,
n-butoxyethyl group, iso-butoxyethyl group, t
Examples include ert-butoxyethyl group, cyclohexyloxyethyl group, methoxypropyl group, ethoxypropyl group, 1-methoxy-1-methyl-ethyl group, 1-ethoxy-1-methyl-ethyl group and the like.

Examples of the trialkylsilyl group include those having 1 to 6 carbon atoms in each alkyl group such as trimethylsilyl group.

As the acid labile group, tert-butyl derivatives other than the above, such as tert-butoxycarbonyl group and tert-butoxycarbonylmethyl group, may be present at the same time.

In the above equation (3), b is 1, 2
Or 3, but preferably b is 2 or 3. By selecting 2 or 3 as b, a hydroxyl group is generated after the acid labile group is decomposed, but the acidity increases as the number of hydroxyl groups increases to 2 or 3, and the alkali dissolution rate can be controlled arbitrarily. Becomes

Further, in the polymer compound having the repeating unit represented by the formula (3), the partial substitution rate of the hydrogen atom of the phenolic hydroxyl group with the acid labile group is 10 to 100 mol% on average as a whole, and particularly 12 to 100%. Mol% is preferable, and when the partial substitution rate of the hydrogen atom of the phenolic hydroxyl group by the acid labile group is less than 10 mol%, the contrast of the alkali dissolution rate becomes small, and the resolution may deteriorate.

In the polymer compound of the above formula (3), the content of the acid labile group affects the contrast of the dissolution rate of the resist film and is related to the characteristics of the resist material such as pattern size control and pattern shape. Is.

Therefore, as described above, m and n are obtained by substituting the hydrogen atom of the phenolic hydroxyl group in the molecule by the acid labile group in an average of 10 to 100 mol%, particularly 12 to 100 mol%. Is a number satisfying such a value, and more preferably 0.1 ≦ m / (m + n) ≦ 1.
It is a number that satisfies 0, particularly 0.12 ≦ m + n ≦ 1.0.

Here, the polymer compound of the above formula (3) is
Considering the characteristics of the chemically amplified positive type resist material compounded with this as a base resin, it is preferable to contain two or more kinds of acid labile groups.

The polymer compound of the above formula (3) has a weight average molecular weight (measurement method is as described below) of 1,000 to
1,000,000, preferably 3,000 to 30,0
It is preferably 00. Weight average molecular weight is 100
If it is less than 0, the film formability and resolution may be poor.
If it exceeds, 000,000, the resolution may be poor.

Further, in the above-mentioned polymer compound, when the molecular weight distribution (Mw / Mn) is wide, there are low molecular weight and high molecular weight polymers, and when there are many low molecular weight polymers, the heat resistance may decrease. However, when a large amount of high-molecular weight polymer is present, it includes one that is difficult to dissolve in an alkali, which may cause tailing after pattern formation.
Therefore, since the influence of such molecular weight and molecular weight distribution is likely to increase as the pattern rule becomes finer, in order to obtain a resist material suitable for use in fine pattern dimensions, the molecular weight distribution of the polymer compound is 1.0
It is preferable that the monodispersion is about 1.5, especially 1.0 to 1.3.

Known acid generators as component (C)
Can be used, for example, the following general formula (5)       (R )_cMY (5) (Wherein R is the same or different substituted or unsubstituted aromatic group)
Group, for example, a phenyl group, tert-butoxyphenenyl
Group, tert-butylphenyl group, tert-butoxy group
Cycarbonyloxyphenyl group, tert-butoxyca
Rubonyl methoxyphenyl group, tert-butyl dimethyl
Rusilyloxyphenyl group, tetrahydrofuranyloxy
Cyphenyl group, 1-ethoxyethoxyphenyl group, 1-
Propoxyethoxyphenyl group, 1-tert-butoxy
A C ethoxyphenyl group and the like, M is sulfonium or
Is iodonium, Y is p-toluene sulfonate, tri
Fluoromethanesulfonate or straight chain having 1 to 20 carbon atoms
A branched, branched, or cyclic alkyl sulfonate
And c is 2 or 3. ) Of the onium salt
In addition, 1,2,3-tris (methanesulfonyloxy)
Benzene, 1,2,3-tris (trifluoromethane)
Rufonyloxy) benzene, 1,2,3-tris (n-
Butanesulfonyloxy) benzene, 1,2,3-tri
Su (p-toluenesulfonyloxy) benzene, 1,
2,3-tris ((+) 10-camphorsulfonylo
Xy) sulfonic acid ester of pyrogallol such as benzene
Derivative, 2-nitrobenzyl tosylate, 2,6-di
Nitrobenzyl tosylate, 2,4-dinitrobenzyl
Nitrobenzylsulfonic acid derivatives such as tosylate,
3,4,5-Tris (5-diazonaphthoquinone sulfoni
Ruoxy) benzophenone, 3,4,5-tris (4-
Diazonaphthoquinonesulfonyloxy) benzophenone
Diazonaphthoquinone sulfonate derivative, such as
α, α′-bisphenylsulfonyldiazomethane, α,
α'-bis (p-tert-butylphenylsulfoni)
Le) diazomethane, α, α′-bis (p-tert-butene)
Toxyphenylsulfonyl) diazomethane, α, α′-
Α such as biscyclohexylsulfonyldiazomethane,
α'-bisaryl or bisalkylsulfonyldiazo
Methane derivative, further N-trifluoromethanesulfonyl
Phthalimide, N- (p-toluenesulfonyloxy)
Phthalimide, N-trifluoromethanesulfonyloxy
Sisuccinimide, N- (p-toluenesulfonyloxy
Si) Succinimide, N-camphorsulfonyloxy
N-sulfonyloxyimide derivatives such as naphthalimide
And so on. Specifically, the following compounds are preferred
It is used well.

[0042]

[Chemical 8]

The amount of the acid generator added is preferably 0.2 to 20 parts, more preferably 0.5 to 10 parts, relative to 100 parts of the base resin.

In the present invention, as the component (D), a basic compound represented by the above formula (1) or (2) and having a weight average molecular weight of 1,000 to 1,000,000 may be blended. Required.

In this case, another basic compound may be added as the basic compound within the range that does not impair the effects of the present invention. Nitrogen-containing compounds are well known as other basic compounds, and examples thereof include amine compounds or amide compounds having a boiling point of 150 ° C. or higher. Specifically, pyridine, polyvinyl pyridine, aniline, N-methylaniline, N, N-dimethylaniline, o-toluidine, m-
Toluidine, p-toluidine, 2,4-lutidine, quinoline, isoquinoline, formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, 2-pyrrolidone, N- Methylpyrrolidone, imidazole, α-picoline, β-picoline, γ-picoline, o-aminobenzoic acid, m-aminobenzoic acid, p-aminobenzoic acid, 1,2-phenylenediamine, 1,3-
Phenylenediamine, 1,4-phenylenediamine, 2
-Triazine compounds such as quinolinecarboxylic acid, 2-amino-4-nitrophenol, 2- (p-chlorophenyl) -4,6-trichloromethyl-s-triazine. Among these, pyrrolidone, N-methylpyrrolidone, o-aminobenzoic acid, m-aminobenzoic acid, p-aminobenzoic acid and 1,2-phenylenediamine are particularly preferable.

The amount of the other basic compound added is 0 to 10 parts, preferably 0.001 to 1 part with respect to 1 part of the acid generator.
It is 10 parts, more preferably 0.01 to 1 part.

The resist composition of the present invention may further contain (E) a dissolution control agent. The dissolution control agent has a molecular weight of 100 to 1,000, preferably 150 to
A compound having 800 and a compound having two or more phenolic hydroxyl groups in the molecule, in which the hydrogen atom of the phenolic hydroxyl group is substituted with an acid labile group at a rate of more than 0 mol% and less than 100 mol% on average as a whole. To do.

In this case, the replacement ratio of hydrogen atoms of the phenolic hydroxyl group with the acid labile group is more preferably 10 mol% or more, especially 30 mol% or more of the whole phenolic hydroxyl group on average. When it is 0 mol%, edge roughness mainly occurs. The upper limit is 100 mol%, more preferably 80 mol%.

In this case, as the compound having a phenolic hydroxyl group, compounds represented by the following formulas (6) to (16) are preferable.

[0050]

[Chemical 9]

[0051]

[Chemical 10]

[0052]

[Chemical 11] (Wherein R ¹⁰ and R ¹¹ are each a hydrogen atom or a linear or branched alkyl group or alkenyl group having 1 to 8 carbon atoms, and R ¹² is a hydrogen atom or a linear chain having 1 to 8 carbon atoms. Or branched alkyl group or alkenyl group, or-(R
¹⁶ ) _s- COOH, R ¹³ and R ¹⁴ are each an alkylene group having 1 to 10 carbon atoms, an arylene group, a carbonyl group, a sulfonyl group, an oxygen atom or a sulfur atom, and R ¹⁵ is an alkyl group having 1 to 8 carbon atoms. , An alkenyl group, a hydrogen atom, a phenyl group or a naphthyl group each substituted with a hydroxyl group, and R ¹⁶ is a linear or branched alkylene group having 1 to 10 carbon atoms. Further, h is an integer of 0 to 2, and z is 0.
Or 1. x, y, x ', y', x ", and y" are x + y = 8, x '+ y' = 5, x "+ y", respectively.
= 4 and has at least one hydroxyl group in each phenyl skeleton. )

In the above formula, R ¹⁰ and R ¹¹ are, for example, hydrogen atom, methyl group, ethyl group, propyl group, butyl group, ethynyl group, cyclohexyl group, and R ¹² are, for example, hydrogen atom, methyl group and ethyl group. , Propyl group, butyl group,
Or cyclohexyl group, -COOH, -CH ₂ COO
Examples of H, R ¹³ and R ¹⁴ include methylene group, ethylene group, phenylene group, carbonyl group, sulfonyl group, oxygen atom, sulfur atom and the like, and examples of R ¹⁵ include methyl group, ethyl group, butyl group and propyl group. , An ethynyl group, a cyclohexyl group, a hydrogen atom, a phenyl group substituted with a hydroxyl group, a naphthyl group, and the like.

Here, the acid labile group of the dissolution control agent is a group represented by the above general formula (4), a tert-butyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, a trialkylsilyl group, a β-ketoalkyl group. Groups and the like.

The component (E) (dissolution control agent) is compounded in an amount of 0 to 50 parts, preferably 5 to 50 parts, and more preferably 10 to 30 parts per 100 parts of the base resin, either alone or in combination of two kinds. The above can be mixed and used. If the content is less than 5 parts, the resolution may not be improved, and if it exceeds 50 parts, the pattern film may be reduced and the resolution may be deteriorated.

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

The chemically amplified positive resist material of the present invention is
In place of or in combination with the dissolution control agent of the component (E), the weight average molecular weight of the (F) dissolution control agent is 1,0.
More than 00 and less than 3,000, and the hydrogen atom of the phenolic hydroxyl group of the compound having a phenolic hydroxyl group in the molecule is more than 0 mol% and less than 100 mol% on average as a whole due to the acid labile group, preferably 0 mol. %, And a compound partially substituted at a ratio of 40 mol% or less can be blended. When it is 0 mol%, a sufficient dissolution control effect cannot be obtained.

In this case, the compound in which the hydrogen atom of the phenolic hydroxyl group is partially substituted by the acid labile group is
One or more compounds selected from compounds having a repeating unit represented by the following general formula (17) are preferable.

[0059]

[Chemical 12] (However, in the formula, R represents an acid labile group, and d and e are numbers satisfying 0 <d / (d + e) ≦ 0.6, respectively.)

Here, the acid labile group of the dissolution control agent is a group represented by the above general formula (4), a tert-butyl group, a tetrahydropyranyl group, a triallylsilyl group,
Further, a β-ketoalkyl group and the like can be mentioned.

The amount of the above-mentioned dissolution control agent (F) to be blended is 0 to 50 parts, more preferably 1 to 50 parts, relative to 100 parts of the base resin.
The range is preferably 50 parts, and more preferably 1 to 30 parts. If the blending amount is too small, the resolution may not be sufficiently improved, and if it exceeds 50 parts, the film thickness of the pattern may be reduced and the resolution may be lowered.

The above-mentioned dissolution control agent (F) can be synthesized by chemically reacting a compound having a phenolic hydroxyl group with an acid labile group similarly to the base resin.

As described above, the dissolution control agent of component (E) and the dissolution control agent of component (F) may be used alone or in combination of both components.

In addition to the above components, the resist composition of the present invention may contain, as an optional component, a surfactant for improving the coating property, a light absorbing material for reducing the influence of diffused reflection from the substrate, and the like. . 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.

In this case, examples of the surfactant include perfluoroalkyl polyoxyethylene ethanol, fluorinated alkyl ester, perfluoroalkylamine oxide, perfluoroalkyl EO adduct and the like, and examples of the light absorbing material include diarylsulfone. Oxide,
Diaryl sulfone, 9,10-dimethylanthracene, 9-fluorenone and the like can be mentioned.

A pattern can be formed by using the chemically amplified positive type resist material of the present invention by adopting a known lithography technique, for example, spin coating on a silicon wafer to form a pattern of 0.5-2. After coating to 0.0 μm and prebaking at 80 to 120 ° C., deep UV,
It can be performed by irradiating a high energy ray such as an electron beam or an X-ray for exposure, followed by post exposure bake (PEB) at 70 to 120 ° C. for 30 to 200 seconds, and then developing with an alkaline aqueous solution. The material of the present invention is particularly suitable for fine patterning with deep ultraviolet rays of 254 to 193 nm and electron beams among high energy rays.

[0067]

The chemically amplified positive resist composition containing the polymer compound of the formula (1) or (2) of the present invention is sensitive to high energy rays, is excellent in sensitivity and resolution, and has a T-value in PED. High resolution without pattern thinning or tailing due to top phenomenon or dark reaction. Therefore, the chemically amplified positive resist composition of the present invention is particularly suitable for K due to these characteristics.
It can be used as a resist material having a small absorption at the exposure wavelength of the rF excimer laser, and can easily form a fine pattern perpendicular to the substrate. Therefore, it is suitable as a fine pattern forming material for VLSI manufacturing.

[0068]

EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples. All parts in each example are parts by weight.

[Examples and Comparative Examples] Basic compounds (Amino Polym.1 to 4) shown below and polyhydroxystyrene (Polym.1 to 7) partially having hydroxyl groups protected by acid labile groups are used as bases. Used as a resin, an acid generator represented by the following formulas (PAG.1 to 3) and a dissolution control agent represented by the following formulas (DRI.1 and 2) are mixed with ethyl lactate (EL) and butyl acetate (BA). A resist solution was dissolved in a solvent (mixing weight ratio EL: BA = 85: 15), a resist material was prepared, and each composition was filtered with a 0.2 μm Teflon filter to prepare a resist solution.

The obtained resist solution was placed on a silicon substrate for LPC.
It was spin-coated on a substrate having a 2500 Å thick SiN ₄ layer prepared by the VD method. Next, this silicon wafer was baked at 100 ° C. for 90 seconds using a hot plate to make the resist film have a thickness of 0.8 μm.

This was exposed using an excimer laser stepper (Nikon Corporation, NSR-2005EX8A, NA = 0.5), and immediately after the exposure, baking was performed at 110 ° C. for 90 seconds to obtain 2.38% tetramethylammonium hydroxide. It was possible to obtain a positive pattern by developing with the aqueous solution.

The exposure after exposure (PED) experiment was carried out by using an excimer laser stepper, and after exposure for 1 hour under an environment in which the NH ₃ concentration in the atmosphere was 20 ppb, the temperature was 90 ° C. at 110 ° C.
After baking for 2 seconds, development was performed for 60 seconds with an aqueous solution of 2.38% tetramethylammonium hydroxide to obtain a positive pattern.

The obtained resist pattern was evaluated as follows. The results are shown in Tables 1 and 2. Evaluation method : First, the sensitivity (Eth) was determined. Then 0.3
The exposure amount for resolving a 5 μm line and space at a ratio of 1: 1 was taken as the optimum exposure amount (Eop), and the minimum line width of the separated line and space in this exposure amount was taken as the resolution of the evaluation resist. The shape of the resolved resist pattern was observed using a scanning electron microscope. Further, the shape of the 0.30 μm pattern of the wafer left for 1 hour after the exposure with the same exposure amount was measured with a scanning electron microscope.

The chemically amplified positive resist material of the present invention is
It was confirmed that the film had good sensitivity and high resolution, that the pattern shape was good, and that there was no film loss, skirting, and T-top phenomenon.

[0075]

[Chemical 13]

[0076]

[Chemical 14]

[0077]

[Chemical 15]

[0078]

[Chemical 16]

[0079]

[Chemical 17]

[0080]

[Table 1]

[0081]

[Table 2]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI H01L 21/027 H01L 21/30 502R (72) Inventor Shigehiro Nagura 28-1 Nishifukushima Nishikofukushima, Kubiki Village, Nakakubiki District, Niigata Prefecture Shin-Etsu Chemical Co., Ltd. Synthetic Technology Laboratory Co., Ltd. (72) Inventor Toshinori Ishihara 28-1 Nishifukushima, Kubiki Village, Nakakubiki-gun, Niigata Prefecture Shin-Etsu Chemical Co., Ltd. Synthetic Technology Laboratory (56) Reference JP-A-1-300247 (JP, A ) JP-A-4-75062 (JP, A) JP-A-6-266110 (JP, A) JP-A-7-128859 (JP, A) JP-A-7-134419 (JP, A) JP-A-7- 319163 (JP, A) JP 8-123030 (JP, A) JP 58-76827 (JP, A) JP 63-124046 (JP, A) JP 7-508840 (JP, A) (58) investigated the field (Int.Cl. ^7, DB ) G03F 7/039 501 G03F 7/004 501 G03F 7/004 503 G03F 7/029 G03F 7/033 H01L 21/027

Claims (6)

(57) [Claims] 1. A compound represented by the following general formula (1) or (2):
A chemically amplified positive resist composition comprising a polymer compound having a weight average molecular weight of 1,000 to 1,000,000. [Chemical 1] (However, in the formula, R ¹ and R ³ are each independently a hydrogen atom or a linear alkyl group having 1 to 10 carbon atoms, and R ² is 1 carbon atom.
10 is a linear or branched alkylene group, and a is 0 or 1. Further, p and q are 0.2 ≦ p / p + q ≦
It is a number that satisfies 1, and p + q and r are numbers that satisfy the above weight average molecular weight. ) 2. The (A) organic solvent (B) base resin comprising a repeating unit represented by the following general formula (3) and having a weight average molecular weight of 1,000 to 1
A polymer compound which is 0,000. [Chemical 2] (However, in the formula, R ⁴ is a hydrogen atom or a linear alkyl group having 1 to 10 carbon atoms, R ⁵ is a hydrogen atom or an acid labile group, and at least one is an acid labile group, m and n are
The hydrogen atom of the phenolic hydroxyl group in the molecule is a number satisfying the value in which the average of the hydrogen atoms of the phenolic hydroxyl group is substituted by the acid labile group as a whole at an average of 10 to 100 mol%, and b is 1, 2 or 3. ) (C) Acid generator (D) The polymer compound (E) according to claim 1 has a molecular weight of 100 to 1,000 as the dissolution controller.
And a compound having two or more phenolic hydroxyl groups in the molecule, in which the hydrogen atom of the phenolic hydroxyl group is replaced by an acid labile group at a rate of more than 0 mol% and not more than 100 mol% on average as a whole. A chemically amplified positive resist material characterized by the following: 3. A weight average molecular weight of 1) as an organic solvent (B), a base resin (C) according to claim 2, an acid generator (D) according to claim 1, and a polymer compound (F) as a dissolution control agent according to claim 1. More than 1,000 and less than 3,000, and the hydrogen atom of the phenolic hydroxyl group of the compound having a phenolic hydroxyl group in the molecule is more than 0 mol% and more than 100 on average as a whole due to the acid labile group.
A chemically amplified positive type resist material comprising a compound partially substituted at a ratio of not more than mol%. 4. (A) Organic solvent (B) The base resin according to claim 2 (C) Acid generator (D) The polymer compound according to claim 1 (E) Dissolution control agent having a molecular weight of 100 to 1 1,000
A compound (F) in which the hydrogen atom of the phenolic hydroxyl group of the compound having two or more phenolic hydroxyl groups in the molecule is replaced with an acid labile group at a rate of more than 0 mol% and less than 100 mol% on average Another dissolution control agent having a weight average molecular weight of 100
The number of hydrogen atoms of the phenolic hydroxyl group of the compound having a phenolic hydroxyl group in the molecule of more than 0 and 3,000 or less exceeds 0 mol% on average as a whole due to the acid labile group and 1
A chemically amplified positive resist material comprising a compound partially substituted at a ratio of not more than 00 mol%. 5. The chemically amplified positive resist composition according to claim 2, wherein the base resin as the component (B) is a monodisperse polymer having a molecular weight distribution of 1.0 to 1.5. 6. The chemically amplified positive resist composition according to claim 2, wherein the acid generator as the component (C) is an onium salt.