JP2002107933A - Resist material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resist material excellent in resolving power and dry etching resistance in exposure with EB(electron beam), EUV(extreme-ultraviolet radiation) or X-rays. SOLUTION: The resist material contains a polymer having repeating units each containing a naphthalene ring having one or more hydroxy groups represented by formula (1) ( where R1 is H, a 1-20C linear, branched or cyclic alkyl or a 6-20C aryl and (a) is an integer of 1-5) and repeating units each having a group obtained by substituting an acid-labile group for the hydrogen atom of the hydroxyl group of a carboxyl group. Since the resist material is excellent in stability when allowed to stand in vacuum after exposure with electron beams, causes slight trailing on a Cr substrate and is excellent in sensitivity, resolution and plasma etching resistance, it is suitable for use as a fine pattern forming material particularly in mask substrate working.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel resist material suitable for fine processing technology and having excellent resolution and dry etching resistance, and particularly to a chemically amplified positive resist material.

[0002]

2. Description of the Related Art LSI
With the high integration and high speed of the pattern, the miniaturization of the pattern rule is rapidly progressing. In 1994, the mass production of 0.18μm rule devices on the SIA roadmap was 200
It was said to be one year, but in fact two years ahead of schedule, 199
Mass production began in 9 years. 0.18μm device is ArF
Although lithography was regarded as a favorite, KrF lithography has been extended, and the 0.15 μm generation,
Mass production by KrF lithography is being studied even for μm. As KrF lithography has matured, acceleration of miniaturization has been spurred. ArF is expected microfabrication 100 nm, F ₂ is 70nm is expected, further ahead is a reduction projection exposure EB (PREVAIL, SC
ALPEL) and EUV using soft X-rays as light sources are candidates.

[0003] Conventionally, the polymer for the resist material has changed greatly each time the wavelength of light has changed. This is to ensure the necessary transmittance. For example, i
In the line, the base of the photosensitizer changed from benzophenone type to non-benzophenone type. The transition from i-line to KrF was accompanied by a change from long-used novolak resins to hydroxystyrene-based resins. The transition from KrF to ArF is dramatic, and since the polymer having a double bond does not transmit light at all, it is changed to an alicyclic polymer. Further, in order to further improve the transmittance of F ₂ , an alicyclic polymer into which a fluorine atom is introduced, such as polytetrafluoroethylene, is being studied.

However, in the case of very short wavelength high energy rays such as EB and X-rays, light elements such as hydrocarbons used in resist materials have no absorption at all.
For the first time, you will be free from transmittance constraints.

The resist material for EB has been practically used for mask drawing, but in recent years, mask manufacturing technology has come to be regarded as a problem. Since the g-line era, reduction projection exposure apparatuses have been used, and the reduction magnification is 1 /.
However, recently, 1/4 magnification has come to be used with the enlargement of the chip size and the enlargement of the diameter of the projection lens. Not only does line width shrink due to the progress of microfabrication,
Reduction of the line width by changing the magnification is a major problem for mask fabrication technology.

In the exposure apparatus for producing a mask, an exposure apparatus using an electron beam (EB) has been used instead of an exposure apparatus using a laser beam in order to increase the line width accuracy. Further, by further increasing the accelerating voltage in the EB electron gun, further miniaturization becomes possible.
From 10 keV to 30 keV, recently 50 keV is becoming mainstream.

Here, as the accelerating voltage increases, there has been a problem of lowering the sensitivity of the resist material. When the acceleration voltage is improved, the influence of forward scattering in the resist film is reduced, so that the contrast of the electron drawing energy is improved and the resolution and dimensional controllability are improved. As a result, the sensitivity of the resist material decreases. Since the mask exposure machine exposes with a single stroke of direct drawing,
A decrease in the sensitivity of the resist material leads to a decrease in productivity, which is not preferable.

[0008] Therefore, in view of the demand for higher sensitivity, a chemically amplified resist material has been studied.

With the improvement of the acceleration voltage and the application of a high-contrast chemically amplified resist material, a 500 nm dimension of 125 nm on a wafer with a 1/4 reduction has been accurately drawn. However, KrF extends the life of the device to 130 nm, and the application of ArF is 100
nm and F ₂ is predicted to be 70 nm.
Limit of photolithography by F ₂ is expected to 50nm. The dimension on the mask at this time is 200 nm. At present, it is difficult to control the size of 200 nm only by improving the resolution of the resist material. In the case of optical lithography, thinning of a resist material greatly contributes to improvement in resolution. This is because the planarization of the device has progressed due to the introduction of CMP or the like. In the case of making a mask, the substrate is flat and the substrate to be processed (for example, Cr,
The film thickness of MoSi, SiO ₂ ) is determined for controlling the light blocking ratio and the phase difference. The only way to reduce the thickness is to improve the dry etching resistance of the resist material.

The present invention has been made in view of the above circumstances, and has as its object to provide a resist material having excellent resolution and dry etching resistance in EB, EUV, and X-ray exposure.

[0011]

Means for Solving the Problems and Embodiments of the Invention The present inventors have conducted intensive studies in order to achieve the above object, and as a result, hydroxylvinyl naphthalene and the hydroxyl group of the carboxyl group have been substituted by acid labile groups. It has been found that a resist material containing a polymer obtained by copolymerizing with a monomer in a base polymer has high resolution in EB, EUV and X-rays and high dry etching resistance.

That is, it is generally said that there is a correlation between the carbon density of the resist and the dry etching resistance. For EB writing which is not affected by absorption, a resist material based on a novolak polymer having excellent etching resistance has been developed. However, it is considered that novolak polymer is difficult to control the molecular weight and the degree of dispersion, and is not a material suitable for fine processing. Here, the carbon density of the benzene ring is 92% with respect to the carbon density of 92%, and the material containing the naphthalene ring is expected to have improved dry etching resistance. Originally, the naphthalene ring has not received much attention because of its high light absorption, but it can be said that it is a promising material for ultrashort wavelength exposure, which is not affected by absorption.

In addition, in soft X-ray (EUV) exposure at a wavelength of 5 to 20 nm, which is expected as an exposure method in fine processing 70 nm or more along with F ₂ exposure,
It has been found that the absorption of carbon atoms is low. It has been found that increasing the carbon density is effective not only in improving the dry etching resistance but also in improving the EUV transmittance.

As a result of further studies based on such findings, the present inventor has found that a repeating unit containing a naphthalene ring having a hydroxy group and a group in which a hydrogen atom of a hydroxyl group of a carboxyl group is substituted by an acid labile group. The inventors have found that a resist material containing a polymer obtained by copolymerizing a repeating unit having the formula (1) can effectively achieve the above object, and have accomplished the present invention.

Accordingly, the present invention provides the following resist material and pattern forming method. Claim 1: A repeating unit having a repeating unit containing a naphthalene ring having a hydroxy group represented by the following general formula (1) and a repeating unit having a group in which a hydrogen atom of a hydroxyl group of a carboxyl group is substituted by an acid labile group. A resist material comprising a coalescence.

Embedded image (In the formula, R ¹ is a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and a is an integer of 1 to 5. Claim 2: In the polymer described in claim 1, the repeating unit having a group in which a hydrogen atom of a hydroxyl group of a carboxyl group is substituted by an acid labile group is represented by the following general formula (2)-
A resist material represented by any one of 1 to (2) -4.

Embedded image (Wherein, R ² represents a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and R ³ represents an acid labile group. b is 0 or 1, X and Y are a single bond or a linear, branched or cyclic divalent hydrocarbon group having 1 to 10 carbon atoms;
The group may include a hydroxy, acetyl or ester group. Z is an oxygen atom or a -NR- group (R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms). Claim 3: The resist material according to claim 1 or 2, wherein the polymer further contains a repeating unit represented by the following general formula (1 ').

Embedded image (In the formula, R ¹ , R ³ , and a have the same meaning as described above.) Claim 4: (A) The polymer according to claim 1, 2 or 3, which is alkali-insoluble or hardly soluble. An electron beam, an X-ray, or a soft X-ray, comprising a base resin which becomes alkali-soluble when the acid labile group is eliminated, (B) an organic solvent, and (C) an acid generator. Chemically amplified positive resist material for exposure. Claim 5: The chemically amplified positive resist material for electron beam, X-ray or soft X-ray exposure according to claim 4, further comprising (D) a basic compound. Claim 6: The electron beam, X-ray or soft X according to claim 4 or 5, further comprising (E) a dissolution inhibitor.
Chemically amplified positive resist material for line exposure. Claim 7: (1) a step of applying the chemically amplified positive resist material according to any one of claims 4, 5, and 6 on a substrate; and (2) a heat mask followed by a photomask. Characterized by comprising a step of exposing with an electron beam, an X-ray or a soft X-ray having a wavelength of 300 nm or less, and (3) a step of performing a heat treatment as necessary and then developing with a developing solution. Forming method.

Hereinafter, the present invention will be described in more detail.
The resist material of the present invention is particularly suitable as a chemically amplified positive resist material. As the base resin, a repeating unit containing a naphthalene ring having a hydroxy group represented by the following general formula (1) and a hydroxyl group of a carboxyl group are used. And a repeating unit having a group in which a hydrogen atom is substituted by an acid labile group.

[0017]

Embedded image

Here, R ¹ is a hydrogen atom, having 1 to 2 carbon atoms.
It is a linear, branched or cyclic alkyl group of 0 or an aryl group having 6 to 20 carbon atoms, and a is an integer of 1 to 5. In this case, as the alkyl group, a methyl group,
Ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, n-pentyl group, n-hexyl group, cyclopropyl group, cyclopropylmethyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, octyl group, Examples of the aryl group include a phenyl group, a methylphenyl group, an ethylphenyl group, a naphthyl group, a methylnaphthyl group, and an ethylnaphthyl group.

On the other hand, a repeating unit having a group in which a hydrogen atom of a hydroxyl group of a carboxyl group is substituted by an acid labile group is represented by any of the following formulas (2) -1 to (2) -4: Is mentioned.

[0020]

Embedded image (Wherein, R ² represents a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and R ³ represents an acid labile group. b is 0 or 1, X and Y are a single bond or a linear, branched or cyclic divalent hydrocarbon group having 1 to 10 carbon atoms;
The group may include a hydroxy, acetyl or ester group. Z is an oxygen atom or a -NR- group (R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms). )

In this case, examples of the alkyl group and aryl group of R ² include the same alkyl groups and aryl groups as those exemplified for R ¹ . Examples of the divalent hydrocarbon group of X and Y include an alkylene group, an arylene group, and an alkylene group which may contain a hydroxy group (OH), an acetyl group (CH ₃ CO), an ester group (COO), and the like. Examples include a group bonded to an arylene group, an ethylene group,
Examples include a propylene group, a hexylene group, a cyclohexylene group, a phenylene group, and a phenylpropylene group.

Further, the above-mentioned polymer can further contain a repeating unit represented by the following general formula (1 ′).

[0023]

Embedded image (In the formula, R ¹ , R ³ and a have the same meanings as described above.)

As the acid labile group for R ³ , various ones are selected. Particularly, as the acid labile group to be substituted for a hydrogen atom of a hydroxyl group of a carboxyl group, a tertiary alkyl group represented by the following formula (3) is used. Preferably, there is.

[0025]

Embedded image

In equation (3), R^Four, R^Five, R⁶Is on
Note R¹Linear or branched having 1 to 20 carbon atoms similar to
Is a cyclic alkyl group or an aryl group having 6 to 20 carbon atoms
But heteroatoms such as oxygen, sulfur, nitrogen and fluorine
And R^FourAnd R^Five, R ^FourAnd R⁶, R^FiveAnd R⁶Is
They may combine together to form a ring.

In the formula (3), R ⁴ , R ⁵ and R ⁶ are a phenyl group, a p-methylphenyl group, a p-ethylphenyl group,
-An unsubstituted or substituted aryl group such as an alkoxy-substituted phenyl group such as a methoxyphenyl group, an aralkyl group such as a benzyl group or a phenethyl group, or a hydrogen atom having an oxygen atom in these groups or a hydrogen atom bonded to a carbon atom; Or a group such as an alkyl group represented by the following formula which forms a carbonyl group by substitution of two hydrogen atoms with an oxygen atom.

That is, in the general formula (3), R ⁴ , R ⁵ , R
⁶ can also be exemplified as an oxoalkyl group having 4 to 20 carbon atoms, and is a 3-oxoalkyl group or the following formula (5) -1 to
And the group represented by (5) -7.

[0029]

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The tertiary alkyl group represented by the formula (3) includes a tert-butyl group, a triethylcarbyl group,
Ethylnorbonyl group, 1-methylcyclohexyl group, 1
-Ethylcyclopentyl group, 2- (2-methyl) adamantyl group, 2- (2-ethyl) adamantyl group, ter
t-amyl group, or the following formulas (4) -1 to (4)-
17 can be specifically mentioned.

[0031]

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Here, R ⁹ represents a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 20 carbon atoms, and specifically, methyl, ethyl, propyl Group, isopropyl group, n-butyl group, sec-butyl group, n-pentyl group, n-hexyl group, cyclopropyl group, cyclopropylmethyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, phenyl group, methylphenyl group, Examples thereof include an ethylphenyl group, a naphthyl group, a methylnaphthyl group, and an ethylnaphthyl group. R ¹⁰ represents a linear, branched or cyclic alkyl group having 2 to 6 carbon atoms, specifically, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and an n-pentyl group. , N-hexyl group, cyclopropyl group, cyclopropylmethyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group and the like. R ¹¹ and R ¹² represent a hydrogen atom, a monovalent hydrocarbon group which may contain a heteroatom having 1 to 6 carbon atoms, or a monovalent hydrocarbon group which may intervene through a heteroatom having 1 to 6 carbon atoms. Examples of the hetero atom include an oxygen atom, a sulfur atom, and a nitrogen atom.
-OR (R is an alkyl group, the same applies hereinafter), -O-, -S
-, - S (= O) -, - NH 2, -NHR, -NR 2, -
It can be contained or intervened as NH-, -NR-.

Examples of R ¹¹ and R ¹² include a hydrogen atom, an alkyl group, a hydroxyalkyl group, an alkoxy group, an alkoxyalkyl group and the like.
It may be branched or annular. Specifically, methyl, hydroxymethyl, ethyl, hydroxyethyl, propyl, isopropyl, n-butyl, se
c-butyl group, n-pentyl group, n-hexyl group, methoxy group, methoxymethoxy group, ethoxy group, tert-
Butoxy groups and the like can be exemplified.

Further, the acid labile group of R ³ has the following formula (4)
-18, (4) As shown in -19, divalent or higher alkylene group, include R ¹⁴ is an arylene group, within the molecule or between molecules of the polymer may be crosslinked. R ^{10 in the} formula (4) -19 is an alkyl group having 1 to ¹⁰ carbon atoms or an aryl group having 6 to 10 carbon atoms, and R ¹⁴ is
It represents a 20 linear, branched or cyclic alkylene group or an arylene group having 6 to 20 carbon atoms, and may contain a hetero atom such as an oxygen atom, a sulfur atom, or a nitrogen atom. c is an integer of 1 to 3. Examples of the alkylene group and arylene group for R ¹⁴ include those in which one hydrogen atom has been eliminated from the alkyl group and aryl group for R ¹ , and the same heteroatoms as described above.

[0035]

Embedded image

Here, there is a problem that the EB drawing has a lower throughput than the light exposure. For example, in the case of mask writing, the number of writing patterns has been particularly increasing in recent years due to the miniaturization of patterns and the introduction of serif patterns of OPC, and writing may take nearly 20 hours. in this case,
The drawing start place is left in vacuum for 20 hours after drawing. In the chemically amplified resist material, the acid labile group in the exposed portion of the resist film is eliminated by heating after exposure (PEB) to improve the solubility in alkali, but the elimination reaction gradually proceeds even at room temperature. I do. In particular, the tertiary ester substituent undergoes an elimination reaction in an environment free from moisture, so that the sensitivity is increased by leaving it in a vacuum (formula (b)).
In particular, a substituent having a lower activation energy for elimination is more remarkably improved in sensitivity by leaving it in a vacuum after drawing. The Cr substrate for mask drawing is formed by a method such as sputtering. However, in the case of a positive resist material, the line becomes thick near the substrate, and a footing pattern occurs. In particular, when a substituent having a high activation energy is used, the tailing phenomenon is remarkable. A substituent having a high activation energy is advantageous when left in vacuum after drawing, but is disadvantageous in preventing footing on the substrate.

Here, an example of the substituent having a low activation energy is an acetal group. The hemming of the board
This is considered to be the same phenomenon as that occurring in a basic substrate such as TiN in KrF lithography. At this time, it is effective to use a substituent having a low activation energy in an elimination reaction such as an acetal group to reduce tailing. Was.
Here, the elimination reaction of the acetal is a reversible reaction, and the elimination does not proceed in the absence of moisture (formula (a) -1). The acetal group lowers the sensitivity when left in a vacuum. By combining a tertiary ester group with low activation energy, which increases sensitivity by leaving it in vacuum after drawing, and an acetal group, which reduces sensitivity, sensitivity sensitivity is improved, and it is resistant to contamination from the substrate. It is possible to obtain a resist material that is strong against pattern abnormalities such as pulling.

[0038]

Embedded image

The acetal group can be represented by the general formula (5).

[0040]

Embedded image

Here, R ¹⁷ has the same carbon number of 1 to 2 as R ^1.
0, a linear, branched or cyclic alkyl group, or an aryl group having 6 to 20 carbon atoms, oxygen, sulfur, nitrogen,
It may contain a hetero atom such as fluorine.

R ¹⁵ and R ^{16 each} represent a hydrogen atom or a group having 1 to 2 carbon atoms.
0 linear, branched or cyclic alkyl group;
It may contain a heteroatom such as oxygen, sulfur, nitrogen, fluorine and the like, and R ¹⁵ and R ¹⁶ , R ¹⁵ and R ¹⁷ , and R ¹⁶ and R ¹⁷ may be respectively bonded to form a ring.

A specific acetal group is represented by the following formula (6)
1 to (6) -25.

[0044]

Embedded image

[0045]

Embedded image

Further, an intermolecular or intramolecularly crosslinked acetal group represented by the general formula (6) -26a or (6) -26b can also be used.

[0047]

Embedded image

In the formula, R ¹⁹ and R ²⁰ represent a hydrogen atom or a carbon atom
Represents a straight-chain, branched or cyclic alkyl group of 1 to 8; Or, R ¹⁹ and R ²⁰ may combine to form a ring,
When a ring is formed, R ¹⁹ and R ^{20 each} represent a linear or branched alkylene group having 1 to 8 carbon atoms. R ²¹ has 1 to 1 carbon atoms
10 linear, branched or cyclic alkylene groups, d is 1
And integers e and f are 0 or an integer of 1 to 10. A
Represents an a-valent aliphatic or alicyclic saturated hydrocarbon group having 1 to 50 carbon atoms, an aromatic hydrocarbon group or a heterocyclic group,
In these groups, a hetero atom may be interposed, or a part of the hydrogen atom bonded to the carbon atom may be substituted by a hydroxyl group, a carboxyl group, a carbonyl group or a fluorine atom. B represents -CO-O-, -NHCO-O- or -NHCONH-.

The crosslinked acetal represented by the general formulas (6) -26a and (6) -26b is specifically represented by the following formula (7)
-1 to (7) -8.

[0050]

Embedded image

As a method for introducing an acetal group, it is preferable to substitute a hydrogen atom of a phenolic hydroxyl group. Although it is possible to substitute the hydrogen atom of the hydroxyl group of the carboxyl group, there is a disadvantage that the storage stability is poor. In the case of the present invention, a method in which the hydrogen atom of OH of the hydroxynaphthyl group is replaced with an acetal (that is, R ³ in the formula (1 ′) is an acetal group), the hydrogen atom of the hydroxyl group of polyhydroxystyrene and the novolak resin is acetal There is a method of blending a polymer substituted with a.

The phenolic hydroxyl group has the following formula (8)
It is also possible to introduce an acid labile group represented by -1 to (8) -9.

[0053]

Embedded image

In the formula, R ²² is the same or different and has 1 to 8 carbon atoms.
Represents a linear, branched or cyclic alkyl group or an aryl group having 6 to 20 carbon atoms. R ²³ is absent or represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. R ²⁴ represents a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, or an aryl group having 6 to 20 carbon atoms.

The polymer of the present invention can be obtained by copolymerizing hydroxyvinylnaphthalene and an acid-labile group-substituted carboxyl group-containing monomer. A monomer for improving the etching resistance and a (meth) acrylate monomer can be further added for polymerization. Phenol, acid anhydride, ester (lactone), carbonate,
It contains a hydrophilic substituent such as alcohol, carboxylic acid, carboxylic acid amide, sulfonic acid amide, ketone and the like, and examples of the unit obtained from such a monomer include the following repeating units.

[0056]

Embedded image

[0057]

Embedded image

In the formula, R ²⁵ , R ²⁶ and R ²⁷ are a hydrogen atom, a fluorine atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, or a fluorinated alkyl group.

The molecular weight of the base polymer is preferably in the range of 2,000 to 100,000 in terms of weight average molecular weight. In the polymerization reaction, the type of initiator (or catalyst) and the method of initiation (light, heat, radiation, plasma, etc.) ), Polymerization conditions (temperature, pressure, concentration, solvent, additives), and the like, which are controlled by radicals such as AIBN, radical polymerization, and ionic polymerization (anionic polymerization) using a catalyst such as alkyllithium. Is common. These polymerizations can be carried out according to the usual methods.

In the above polymer, the content of the unit of the formula (1) is 10 to 95 mol%, preferably 20 to 95 mol%.
The content of a unit having a group in which a hydrogen atom of a hydroxyl group of a carboxyl group is substituted with an acid labile group is preferably 5 mol%, more preferably 30 mol% to 90 mol%.
It is preferable that the content is 60 to 60 mol%, more preferably 7 to 50 mol%, and still more preferably 10 to 40 mol%. Further, the content of the unit of the formula (1 ′) is 0 to 60 mol%, more preferably 0 to 50 mol%, and still more preferably 0 to 40 mol%, and the content of the other units is 0 to 50 mol%. Mole%,
More preferably 0 to 40 mol%, still more preferably 0 to 3 mol%.
It is preferably 0 mol%.

The above polymer has a weight average molecular weight of 2,
It is preferably in the range of 000 to 100,000.

The resist material of the present invention uses the above polymer as a base resin. In particular, when a chemically amplified positive resist material is used, (A) the above polymer, which is alkali-insoluble or hardly soluble, A base resin which becomes alkali-soluble when the acid labile group is eliminated, (B) an organic solvent, and (C) an acid generator, preferably (D) a basic compound and / or (E) It contains an inhibitor.

The organic solvent (B) used in the present invention may be any organic solvent in which the acid generator, base resin, dissolution inhibitor and the like can be dissolved. Examples of such an organic solvent include ketones such as cyclohexanone and methyl-2-n-amyl ketone, 3-methoxybutanol, 3-methyl-3-methoxybutanol,
1-methoxy-2-propanol, 1-ethoxy-2-
Alcohols such as propanol, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, ethers such as diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether Acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate,
Esters such as ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, and propylene glycol-mono-tert-butyl ether acetate are exemplified. The amount of (A) component 1
200 to 5,000 parts by weight, especially 4 parts by weight
It is preferably from 0.00 to 3,000 parts by weight.

Examples of the acid generator (C) include an onium salt of the following general formula (10), a diazomethane derivative of the formula (11), a glyoxime derivative of the formula (12), a β-ketosulfone derivative, a disulfone derivative, and nitrobenzyl. Examples thereof include a sulfonate derivative, a sulfonic ester derivative, and an imido-yl sulfonate derivative, and an acid generator that generates camphorsulfonic acid is particularly preferably used.

[0065] _{^{(R 30) b M + K}} -
(10) (where R ³⁰ is a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, 6 to 12 carbon atoms)
Represents an aryl group or an aralkyl group having 7 to 12 carbon atoms, M ⁺ represents iodonium or sulfonium, K ⁻ represents a non-nucleophilic counter ion, and b is 2 or 3. )

As the alkyl group for R ^30, a methyl group, an ethyl group, a propyl group, a butyl group, a cyclohexyl group,
An oxocyclohexyl group, a norbornyl group, an adamantyl group and the like can be mentioned. As the aryl group, a phenyl group,
p-methoxyphenyl group, m-methoxyphenyl group, o
-Methoxyphenyl group, ethoxyphenyl group, p-te
an alkoxyphenyl group such as an rt-butoxyphenyl group, an m-tert-butoxyphenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group,
Ethylphenyl group, 4-tert-butylphenyl group,
Examples thereof include an alkylphenyl group such as a 4-butylphenyl group and a dimethylphenyl group. Examples of the aralkyl group include a benzyl group and a phenethyl group. K ^- a non-nucleophilic counter chloride ions as the ion, halide ions such as bromide ion, camphorsulfonate, norbornene sulfonates, cyclic alkyl sulfonates such as adamantane sulfonate, triflate, 1,1,1-trifluoroethane sulfonate, Fluoroalkyl sulfonates such as nonafluorobutane sulfonate, tosylate, benzene sulfonate, 4-fluorobenzene sulfonate, 1,2,3,4,5-pentafluorobenzene sulfonate, 1-naphthyl sulfonate, 2-naphthyl sulfonate, p-methoxybenzene Sulfonate, m-methoxybenzenesulfonate, p-fluorobenzenesulfonate, p-tert butoxybenzenesulfonate, p-tosyloxybenzylsulfonate,
Examples include arylsulfonates such as p-phenyloxybenzenesulfonate, p-benzyloxybenzenesulfonate, p-pivaloyloxybenzenesulfonate, and alkylsulfonates such as mesylate and butanesulfonate.

[0067]

Embedded image (However, R ³¹ and R ³² are a linear, branched or cyclic alkyl group or halogenated alkyl group having 1 to 12 carbon atoms, an aryl group or halogenated aryl group having 6 to 12 carbon atoms, or a C ⁷ to C 12 12 represents an aralkyl group)

As the alkyl group for R ³¹ and R ³² , 10-camphor group, methyl group, ethyl group, propyl group, butyl group, amyl group, cyclopentyl group, cyclohexyl group,
Examples include a norbornyl group and an adamantyl group. Examples of the halogenated alkyl group include a trifluoromethyl group,
Examples thereof include a 1,1-trifluoroethyl group, a 1,1,1-trichloroethyl group, and a nonafluorobutyl group. Examples of the aryl group include a phenyl group, a p-methoxyphenyl group, an m-methoxyphenyl group, an o-methoxyphenyl group, an ethoxyphenyl group, an p-tert-butoxyphenyl group, an alkoxyphenyl group such as a m-tert-butoxyphenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, ethylphenyl group,
Examples thereof include an alkylphenyl group such as a 4-tert-butylphenyl group, a 4-butylphenyl group, and a dimethylphenyl group. Examples of the halogenated aryl group include a fluorobenzene group, a chlorobenzene group, a 1,2,3,4,5-pentafluorobenzene group, and the like. Examples of the aralkyl group include a benzyl group and a phenethyl group.

[0069]

Embedded image (However, R ³³ , R ³⁴ , and R ³⁵ are linear having 1 to 12 carbon atoms;
It represents a branched or cyclic alkyl group or a halogenated alkyl group, an aryl group having 6 to 12 carbon atoms, an aryl halide group or an aralkyl group having 7 to 12 carbon atoms. Also,
R ³⁴ and R ³⁵ may combine with each other to form a cyclic structure, and when forming a cyclic structure, R ³⁴ and R ³⁵ each represent a linear or branched alkylene group having 1 to 6 carbon atoms. . )

As the alkyl group, halogenated alkyl group, aryl group, halogenated aryl group and aralkyl group of R ³³ , R ³⁴ and R ³⁵ , the same groups as described for R ³¹ and R ³² can be mentioned. The alkylene group for R ³⁴ and R ³⁵ includes a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group and the like. Specifically, for example, diphenyliodonium camphorsulfonate, camphorsulfonic acid (p-tert-butoxyphenyl)
Phenyliodonium, diphenyliodonium p-toluenesulfonate, p-toluenesulfonic acid (p-te
rt-butoxyphenyl) phenyliodonium, triphenylsulfonium camphorsulfonate, (p-tert-butoxyphenyl) diphenylsulfonium camphorsulfonate, bis (p-
tert-butoxyphenyl) phenylsulfonium,
Tris (p-tert-butoxyphenyl) sulfonium camphorsulfonate, triphenylsulfonium p-toluenesulfonate, p-toluenesulfonate (p-
tert-butoxyphenyl) diphenylsulfonium, bis (p-tert-butoxyphenyl) phenylsulfonium p-toluenesulfonate, tris (p-tert-butoxyphenyl) sulfonium p-toluenesulfonate, triphenylsulfonium nonafluorobutanesulfonate, Triphenylsulfonium butanesulfonate, trimethylsulfonium camphorsulfonate, trimethylsulfonium p-toluenesulfonate,
Cyclohexylmethyl camphorsulfonate (2-oxocyclohexyl) sulfonium, cyclohexylmethyl p-toluenesulfonate (2-oxocyclohexyl) sulfonium, dimethylphenylsulfonium camphorsulfonate, dimethylphenylsulfonium p-toluenesulfonate, dicyclohexylphenylsulfonium camphorsulfonate Onium salts such as dicyclohexylphenylsulfonium p-toluenesulfonate, bis (camphorsulfonyl) diazomethane, bis (benzenesulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, bis (xylenesulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane , Bis (cyclopentylsulfonyl)
Diazomethane, bis (n-butylsulfonyl) diazomethane, bis (isobutylsulfonyl) diazomethane, bis (sec-butylsulfonyl) diazomethane, bis (n-propylsulfonyl) diazomethane, bis (isopropylsulfonyl) diazomethane, bis (tert-
(Butylsulfonyl) diazomethane, bis (n-amylsulfonyl) diazomethane, bis (isoamylsulfonyl) diazomethane, bis (sec-amylsulfonyl)
Diazomethane, bis (tert-amylsulfonyl) diazomethane, 1-cyclohexylsulfonyl-1- (t
tert-butylsulfonyl) diazomethane, 1-cyclohexylsulfonyl-1- (tert-amylsulfonyl) diazomethane, 1-tert-amylsulfonyl-
Diazomethane derivatives such as 1- (tert-butylsulfonyl) diazomethane, bis-o- (p-toluenesulfonyl) -α-dimethylglyoxime, bis-o- (p-
Toluenesulfonyl) -α-diphenylglyoxime,
Bis-o- (p-toluenesulfonyl) -α-dicyclohexylglyoxime, bis-o- (p-toluenesulfonyl) -2,3-pentanedione glyoxime, bis-o- (p-toluenesulfonyl) -2- Methyl-3,
4-pentanedione glyoxime, bis-o- (n-butanesulfonyl) -α-dimethylglyoxime, bis-
o- (n-butanesulfonyl) -α-diphenylglyoxime, bis-o- (n-butanesulfonyl) -α-dicyclohexylglyoxime, bis-o- (n-butanesulfonyl) -2,3-pentanedione Oximes,
Bis-o- (n-butanesulfonyl) -2-methyl-
3,4-pentanedione glyoxime, bis-o- (methanesulfonyl) -α-dimethylglyoxime, bis-
o- (trifluoromethanesulfonyl) -α-dimethylglyoxime, bis-o- (1,1,1-trifluoroethanesulfonyl) -α-dimethylglyoxime, bis-o- (tert-butanesulfonyl) -α- Dimethylglyoxime, bis-o- (perfluorooctanesulfonyl) -α-dimethylglyoxime, bis-o- (cyclohexanesulfonyl) -α-dimethylglyoxime, bis-o- (benzenesulfonyl) -α-dimethylglyoxime , Bis-o- (p-fluorobenzenesulfonyl) -α-dimethylglyoxime, bis-o- (p
-Tert-butylbenzenesulfonyl) -α-dimethylglyoxime, bis-o- (xylenesulfonyl)-
Glyoxime derivatives such as α-dimethylglyoxime and bis-o- (camphorsulfonyl) -α-dimethylglyoxime, 2-cyclohexylcarbonyl-2- (p-
Β-ketosulfone derivatives such as toluenesulfonyl) propane and 2-isopropylcarbonyl-2- (p-toluenesulfonyl) propane; disulfone derivatives such as diphenyldisulfone and dicyclohexyldisulfone; 2,6-dinitrobenzyl p-toluenesulfonate; Nitrobenzylsulfonate derivatives such as toluenesulfonic acid 2,4-dinitrobenzyl, 1,2,3-tris (methanesulfonyloxy) benzene, 1,2,3-tris (trifluoromethanesulfonyloxy) benzene,
1,2,3-tris (p-toluenesulfonyloxy)
Sulfonate derivatives such as benzene, phthalimido-yl-triflate, phthalimido-yl-tosylate, 5-norbornene-2,3-dicarboximide-
Imido-yl-sulfonate derivatives such as yl-triflate, 5-norbornene-2,3-dicarboximido-yl-tosylate and 5-norbornene-2,3-dicarboximido-yl-n-butylsulfonate; Can be The acid generators may be used alone or in combination of two or more.

The compounding amount of the acid generator is 100 base resin.
0.2 to 15 parts by weight, especially 0.5 to 15 parts by weight
If it is less than 0.2 parts by weight, the amount of acid generated during exposure is small, and the sensitivity and resolution may be poor. If it exceeds 20 parts by weight, the etching resistance of the resist may be poor. .

As the basic compound as the component (D), a compound capable of suppressing the diffusion rate when the acid generated from the acid generator diffuses into the resist film is suitable. By the compounding, the diffusion rate of the acid in the resist film is suppressed, the resolution is improved, the sensitivity change after exposure is suppressed, the dependency on the substrate and the environment is reduced, and the exposure margin and the pattern profile are improved. (JP-A-5-232706, JP-A-5-249683 and JP-A-5-249683).
No. 158239, No. 5-249662, No. 5-25
No. 7282, No. 5-289322, No. 5-28934
No. 0 publication).

Such basic compounds include primary, secondary and tertiary aliphatic amines, hybrid amines,
Aromatic amines, heterocyclic amines, nitrogen-containing compounds having a carboxy group, nitrogen-containing compounds having a sulfonyl group,
Examples of the compound include a nitrogen-containing compound having a hydroxy group, a nitrogen-containing compound having a hydroxyphenyl group, an alcoholic nitrogen-containing compound, an amide derivative, and an imide derivative, and an aliphatic amine is particularly preferably used.

Specifically, the primary aliphatic amines include ammonia, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine,
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, 3-methylaniline, 4-methylaniline, ethylaniline, propylaniline, trimethylaniline, 2-nitroaniline , 3-nitroaniline, 4-nitroaniline, 2,4-dinitroaniline, 2,6-dinitroaniline, 3,5-dinitroaniline, N, N-
Dimethyl toluidine, etc.), diphenyl (p-tolyl) amine, methyl diphenylamine, triphenylamine,
Phenylenediamine, naphthylamine, diaminonaphthalene, pyrrole derivatives (e.g., pyrrole, 2H-pyrrole, 1-methylpyrrole, 2,4-dimethylpyrrole,
2,5-dimethylpyrrole, N-methylpyrrole, etc.),
Oxazole derivatives (eg, oxazole, isoxazole, etc.), thiazole derivatives (eg, thiazole, isothiazole, etc.), imidazole derivatives (eg, imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, etc.), pyrazole derivatives, furazane derivatives, Pyrroline derivatives (eg, pyrroline, 2-methyl-1-pyrroline, etc.), pyrrolidine derivatives (eg, pyrrolidine, N-methylpyrrolidine, pyrrolidinone, N-methylpyrrolidone, etc.), imidazoline derivatives, imidazolidine derivatives, pyridine derivatives (eg, pyridine, methyl) Pyridine, ethylpyridine, propylpyridine, butylpyridine, 4- (1-butylpentyl) pyridine, dimethylpyridine, trimethylpyridine, triethylpyridine, phenylpyridyl , 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, 1H-indazole derivatives, indoline derivatives, quinoline derivatives (Eg, quinoline, 3-quinolinecarbonitrile), isoquinoline derivatives, cinnoline derivatives, quinazoline derivatives, quinoxaline derivatives, phthalazine derivatives, purine derivatives, pteridine derivatives, carbazole derivatives, phenanthridine derivatives, acridine derivatives, phenazine derivatives, 1,1
Examples thereof include 0-phenanthroline derivatives, adenine derivatives, adenosine derivatives, guanine derivatives, guanosine derivatives, uracil derivatives, uridine derivatives and the like.

Further, examples of the nitrogen-containing compound having a carboxy group include aminobenzoic acid, indolecarboxylic acid, and amino acid derivatives (eg, nicotinic acid, alanine, arginine, aspartic acid, glutamic acid, glycine,
Histidine, isoleucine, glycylleucine, leucine, methionine, phenylalanine, threonine, lysine, 3-aminopyrazine-2-carboxylic acid, methoxyalanine, etc.), and 3-pyridinesulfonic acid as a nitrogen-containing compound having a sulfonyl group. , P-toluenesulfonate and the like. Examples of the nitrogen-containing compound having a hydroxy group, the nitrogen-containing compound having a hydroxyphenyl group, and the alcoholic nitrogen-containing compound include 2-hydroxypyridine, aminocresol, and 2,4-quinoline. Diol, 3-indolemethanol hydrate, monoethanolamine, diethanolamine, triethanolamine, N-ethyldiethanolamine, N, N-
Diethylethanolamine, triisopropanolamine, 2,2′-iminodiethanol, 2-aminoethanol, 3-amino-1-propanol, 4-amino-1
-Butanol, 4- (2-hydroxyethyl) morpholine, 2- (2-hydroxyethyl) pyridine, 1- (2
-Hydroxyethyl) piperazine, 1- [2- (2-hydroxyethoxy) ethyl] piperazine, piperidineethanol, 1- (2-hydroxyethyl) pyrrolidine,
1- (2-hydroxyethyl) -2-pyrrolidinone, 3
-Piperidino-1,2-propanediol, 3-pyrrolidino-1,2-propanediol, 8-hydroxyurolidine, 3-quinuclidinol, 3-tropanol,
Examples thereof include 1-methyl-2-pyrrolidineethanol, 1-aziridineethanol, N- (2-hydroxyethyl) phthalimide, and N- (2-hydroxyethyl) isonicotinamide. Examples of amide derivatives include formamide, N-methylformamide, N, N-dimethylformamide, acetamido, N-methylacetamido,
N-dimethylacetamide, propionamide, benzamide and the like are exemplified. Examples of the imide derivative include phthalimide, succinimide, and maleimide.

Further, basic compounds represented by the following general formulas (13) and (14) can be blended.

[0078]

Embedded image (Wherein, R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁷ , and R ⁴⁸ are each independently a linear, branched, or cyclic alkylene group having 1 to 20 carbon atoms, R ⁴⁴ , R ⁴⁵ , R ⁴⁶ , R ⁴⁹ and R ^{50 each} represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an amino group, R ⁴⁴ and R ⁴⁵ , R ⁴⁵ and R ⁴⁶ , R ⁴⁴ and R ⁴⁶ , R ⁴⁴ and R ⁴⁵ and R ⁴⁶ ; R
⁴⁹ and R ⁵⁰ may be combined with each other to form a ring. S,
T and U each represent an integer of 0 to 20. Where S,
When T and U = 0, R ⁴⁴ , R ⁴⁵ , R ⁴⁶ , R ⁴⁹ and R ⁵⁰ do not contain a hydrogen atom. )

Here, the alkylene group represented by R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁷ and R ⁴⁸ has 1 to 20 carbon atoms, preferably 1 carbon atom.
-10, more preferably 1-8, and specifically, methylene, ethylene, n-propylene, isopropylene, n-butylene, isobutylene, n-
Examples include a pentylene group, an isopentylene group, a hexylene group, a nonylene group, a decylene group, a cyclopentylene group, and a cyclohexylene group.

The alkyl group of R ⁴⁴ , R ⁴⁵ , R ⁴⁶ , R ⁴⁹ and R ⁵⁰ has 1 to 20 carbon atoms, preferably 1 to 20 carbon atoms.
8, more preferably 1 to 6, which may be linear, branched, or cyclic. Specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, hexyl, nonyl, decyl, dodecyl Group, tridecyl group, cyclopentyl group, cyclohexyl group and the like. Furthermore,
^R44 and ^R45 , ^R45 and ^R46 , ^R44 and ^R46 , ^R44 and ^R45 and R
^46, and R ⁴⁹ and R ⁵⁰ form a ring, the number of carbon atoms in the ring is 1 to 20, more preferably 1 to 8, more preferably 1 to
And these rings have 1 to 6 carbon atoms, especially 1 to 4 carbon atoms.
May be branched.

S, T and U are each an integer of 0 to 20, more preferably 1 to 10, and further preferably an integer of 1 to 8.

Specific examples of the compounds of the above formulas (13) and (14) include tris {2- (methoxymethoxy) ethyl} amine, tris {2- (methoxyethoxy) ethyl} amine, and tris [2-{( 2-methoxyethoxy)
Methoxy {ethyl] amine, tris {2- (2-methoxyethoxy) ethyl} amine, tris {2- (1-methoxyethoxy) ethyl} amine, tris {2- (1-ethoxyethoxy) ethyl} amine, tris 2- (1-
Ethoxypropoxy) ethyl} amine, tris [2-
{(2-hydroxyethoxy) ethoxy} ethyl] amine, 4,7,13,16,21,24-hexaoxa-
1,10-diazabicyclo [8.8.8] hexacosan, 4,7,13,18-tetraoxa-1,10-diazabicyclo [8.5.5] eicosan, 1,4,1
0,13-tetraoxa-7,16-diazabicyclooctadecane, 1-aza-12-crown-4, 1-aza-15-crown-5, 1-aza-18-crown-6
And the like. Especially tertiary amines, aniline derivatives,
Pyrrolidine derivatives, pyridine derivatives, quinoline derivatives,
Amino acid derivatives, nitrogen-containing compounds having a hydroxy group,
Nitrogen-containing compounds having a hydroxyphenyl group, alcoholic nitrogen-containing compounds, amide derivatives, imide derivatives, tris {2- (methoxymethoxy) ethyl} amine, tris {(2- (2-methoxyethoxy) ethyl} amine, tris [ 2-{(2-methoxyethoxy) methyl} ethyl] amine, 1-aza-15-crown-5 and the like are preferred.

The above-mentioned basic compounds can be used alone or in combination of two or more. The compounding amount is 0.01 to 2 parts by weight, particularly 0 to 2 parts by weight, based on 100 parts by weight of the total base resin. 0.01 to 1 part by weight is preferred. When the amount is less than 0.01 part by weight, the effect of the compounding is not obtained. When the amount exceeds 2 parts by weight, the sensitivity may be excessively lowered.

Next, as the dissolution inhibitor of the component (E),
A compound having a molecular weight of 2,000 or less, whose solubility in an alkali developing solution is changed by the action of an acid, particularly a part or all of a low-molecular-weight phenol or carboxylic acid derivative of 1,500 or less is substituted with an acid-labile substituent. The following compounds can be mentioned.

Examples of the phenol or carboxylic acid derivative having a molecular weight of 1,500 or less include 4,4 '-(1-methylethylidene) bisphenol and [1,1'-biphenyl-4,4'-diol] 2,2'-diol. Methylene bis [4-
Methylphenol], 4,4-bis (4'-hydroxyphenyl) valeric acid, tris (4-hydroxyphenyl)
Methane, 1,1,1-tris (4′-hydroxyphenyl) ethane, 1,1,2-tris (4′-hydroxyphenyl) ethane, phenolphthalein, thymolphthalein, 3,3′difluoro [(1 , 1'biphenyl)
4,4'-diol], 3,3 ', 5,5'-tetrafluoro [(1,1'-biphenyl) -4,4'-diol], 4,4'-[2,2,2- Trifluoro-1-
(Trifluoromethyl) ethylidene] bisphenol,
4,4′-methylenebis [2-fluorophenol],
2,2′-methylenebis [4-fluorophenol],
4,4′-isopropylidenebis [2-fluorophenol], cyclohexylidenebis [2-fluorophenol], 4,4 ′-[(4-fluorophenyl) methylene] bis [2-fluorophenol], 4,4 '-Methylenebis [2,6-difluorophenol], 4,4'
-(4-fluorophenyl) methylenebis [2,6-difluorophenol], 2,6-bis [(2-hydroxy-5-fluorophenyl) methyl] -4-fluorophenol, 2,6-bis [(4- Hydroxy-3-fluorophenyl) methyl] -4-fluorophenol,
2,4-bis [(3-hydroxy-4-hydroxyphenyl) methyl] -6-methylphenol and the like,
As The acid labile substituents are the same as those for R ^3.

The addition amount of the dissolution inhibitor in the resist material of the present invention is not more than 20 parts by weight, preferably not more than 15 parts by weight, based on 100 parts by weight of the solids in the resist material. If the amount is more than 20 parts by weight, the heat resistance of the resist material decreases because the monomer component increases.

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

Here, the surfactant is preferably a nonionic surfactant, and examples thereof include perfluoroalkylpolyoxyethylene ethanol, fluorinated alkyl esters, perfluoroalkylamine oxides, and fluorine-containing organosiloxane compounds. For example, Florard "F
C-430 "," FC-431 "(all manufactured by Sumitomo 3M Limited), Surflon" S-141 "," S-1 "
45, S-381, S-383 (all manufactured by Asahi Glass Co., Ltd.), Unidyne DS-401, DS
-403 "," DS-451 "(all manufactured by Daikin Industries, Ltd.), MegaFac" F-8151 "," F-1
71 "," F-172 "," F-173 "," F-17 "
7 "(all manufactured by Dainippon Ink and Chemicals, Inc.)," X-7
0-092 "and" X-70-093 "(all manufactured by Shin-Etsu Chemical Co., Ltd.). Preferably, Florad “FC-430” (Sumitomo 3M Co., Ltd.)
X-70-093 "(Shin-Etsu Chemical Co., Ltd.)
Is mentioned.

A pattern can be formed using the resist material of the present invention by using a known lithography technique. For example, spin coating or the like is performed on a synthetic quartz substrate on which a Cr film is formed by sputtering. Is applied so that the film thickness becomes 0.1 to 1.0 μm, and then this is applied to a hot plate or a hot oven for 60 to 2 μm.
00 ° C, 10 seconds to 60 minutes, preferably 80 to 150
Pre-bake at 30 ° C for 30 seconds to 5 minutes for a hot plate and 5 to 30 minutes for an oven. Next, to form a target pattern, an electron beam is irradiated so as to have an exposure amount of about 1 to 200 μC, preferably about 2 to 50 μC, and then is irradiated with a hot plate or a hot oven for 60 to 200 μC.
C., for 10 seconds to 60 minutes, preferably 80 to 150.degree. C., and for a hot plate, post exposure bake (PEB) for 30 seconds to 5 minutes. Further, using a developer of 0.1 to 5%, preferably 2 to 3% of an aqueous alkali solution such as tetramethylammonium hydroxide (TMAH), immersion for 10 seconds to 3 minutes, preferably 30 seconds to 2 minutes ( A target pattern is formed on the substrate by developing using a conventional method such as a dip method, a paddle method, or a spray method.

[0090]

The resist material of the present invention is excellent in stability in vacuum standing after exposure in electron beam exposure, has small footing on a Cr substrate, and is excellent in sensitivity, resolution and plasma etching resistance. Therefore, the resist material of the present invention is suitable as a material for forming a fine pattern particularly in processing of a mask substrate due to these characteristics.

[0091]

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

Synthesis Example 1 Copolymerization of 1-hydroxy-5-vinylnaphthalene and t-butyl acrylate (Polymer 1) 100 g of 1-hydroxy-5-vinylnaphthalene and 30 g of t-butyl acrylate in a 2 L flask. Was dissolved in 560 ml of toluene, oxygen in the system was sufficiently removed, 5.5 g of AIBN was charged, and the temperature was raised to 60 ° C. to carry out a polymerization reaction for 24 hours.

In order to purify the obtained polymer, the reaction mixture was poured into a hexane / ether (3: 2) mixed solvent, and the resulting polymer was precipitated and separated. 97 g of a white polymer polyhydroxyvinyl was obtained. A naphthalene-co-t-butyl acrylate copolymer (0.7: 0.3) was obtained.

105 g of the white polymer polyhydroxyvinylnaphthalene-co-t-butyl acrylate thus obtained had a weight average molecular weight of 9800 by a light scattering method.
g / mol, and the degree of dispersion (= Mw
/ Mn) was 1.60.
Further, by measuring ¹ HNMR, it was confirmed that hydroxyvinylnaphthalene and t-butyl acrylate were contained in the polymer at a ratio of about 0.7: 0.3.

[Synthesis Example 2] Copolymerization of 1-hydroxy-5-vinylnaphthalene and ethyl cyclopentyl acrylate (Polymer 2) 100 g of 1-hydroxy-5-vinyl naphthalene and t-ethyl cyclopentyl acrylate in a 2 L flask 40 g was dissolved in 560 ml of toluene, oxygen in the system was sufficiently removed, 5.5 g of AIBN was charged, and the temperature was raised to 60 ° C. to carry out a polymerization reaction for 24 hours.

In order to purify the obtained polymer, the reaction mixture was poured into a hexane / ether (3: 2) mixed solvent, and the obtained polymer was precipitated and separated. 97 g of a white polymer polyhydroxyvinyl was obtained. Naphthalene-co-ethyl cyclopentyl acrylate copolymer (0.
8: 0.2).

The thus obtained 105 g of the white polymer polyhydroxyvinylnaphthalene-co-ethylcyclopentyl acrylate was found to have a weight average molecular weight of 12,000 g / mol by a light scattering method, and the degree of dispersion (= Mw / Mn) was 1.70. Further, by measuring ¹ HNMR, it was confirmed that hydroxyvinylnaphthalene and t-butyl acrylate were contained in the polymer at a ratio of about 0.8: 0.2.

[Synthesis Example 3] 1-Hydroxy-5-vinylnaphthalene and Ethylcyclopentyl acrylate were copolymerized by EOE (polymer 3) 1-Hydroxy-5-vinylnaphthalene obtained in a 2 L flask and acrylic acid 100 g of ethylcyclopentyl ester was dissolved in 1000 ml of tetrahydrofuran, a catalytic amount of methanesulfonic acid was added, and then 10 g of ethoxyvinyl ether was added while stirring at 20 ° C. After reacting for 2 hours, the mixture was neutralized with concentrated aqueous ammonia, and the neutralized reaction solution was added dropwise to 10 L of water to obtain a white solid. After filtration, this was dissolved in 500 ml of acetone, dropped into 10 L of water, filtered, and dried under vacuum to obtain a polymer. From ¹ H-NMR analysis, 5% of the hydroxyl group of naphthalene was replaced by an ethoxyethyl group. I confirmed that.

[Synthesis Examples 4 and 5] Polymers 4 and 5 were synthesized in the same manner as described above.

[Synthesis Examples 6 to 9] (Comparative Example) Polymers 6 to 9 were synthesized according to a conventional method.

[0101]

Embedded image

[0102]

Embedded image

[0103]

Embedded image

Examples and Comparative Examples (1) Preparation of Resist Solution Polymers 1 to 9 and acid generators (PAG1,
2) The dissolution inhibitor (DRI1) and the basic compound were replaced with propylene glycol monomethyl ether acetate (PG
(MEA) and ethyl lactate (EL) at a weight ratio of 1: 1, and well mixed with 800 parts by weight of a solvent containing 100 ppm of a fluorochemical surfactant FC-430 (manufactured by Sumitomo 3M Ltd.). The resist solution was prepared by filtration through a high-density polyethylene filter of 0.1 μm. (2) Drawing evaluation Using a CFS-4ES manufactured by Shibaura Seisakusho Co., a Cr film was sputtered on a 6 inch φ synthetic quartz wafer to 100 n.
Clean track Mar on a substrate made with a thickness of m
A resist solution was spin-coated using k5 (manufactured by Tokyo Electron Limited) and prebaked on a hot plate at 100 ° C. for 90 seconds to form a 500 nm resist film. HV voltage of 30 keV using an EB writing system manufactured by Elionix,
Writing in a vacuum chamber was performed with a beam current of 0.1 A. Immediately after drawing, using a clean track Mark5 (manufactured by Tokyo Electron Limited) on a hot plate at 110 ° C.
Post-exposure baking (PEB) was performed for 90 seconds, and paddle development was performed for 60 seconds with a 2.38 wt% TMAH aqueous solution to obtain a positive pattern.

After the drawing, the sample left in the vacuum chamber of the drawing apparatus for 24 hours was similarly subjected to PEB and development. The dimensions of the pattern were measured using a length measuring SEM, S-7200 (manufactured by Hitachi, Ltd.). The obtained pattern was evaluated as follows. First, an exposure amount at which 0.8 μmL / S is exactly as measured is obtained, and an optimal exposure amount (Eopt) is obtained.
And The wafer was cleaved, and the resist cross-sectional shape at the optimum exposure was observed. Table 1 shows the results.

Next, an etching test was performed using a Cl ₂ / BCl ₃ gas. Using a dry etching apparatus L-507D-L manufactured by Nidec Anelva Co., Ltd., a difference in thickness of the resist before and after etching was determined. Table 2 shows the results. The etching conditions are as shown below. Chamber pressure 40.0 Pa RF power 300 W Gap 9 mm Cl ₂ gas flow rate 30 ml / min BCl ₃ gas flow rate 30 ml / min CHF ₃ gas flow rate 100 ml / min O ₂ gas flow rate 2 ml / min Time 360 sec

[0107]

[Table 1]

[0108]

[Table 2]

[0109]

Embedded image

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 5/00 C08K 5/00 C08L 25/18 C08L 25/18 33/14 33/14 35/06 35 / 06 45/00 45/00 H01L 21/027 H01L 21/30 502R (72) Inventor Takanobu Takeda 28-1 Nishifukushima, Daiku, Nishiki-son, Nakakushiro-gun, Niigata Shin-Etsu Chemical Co., Ltd. Synthetic Technology Laboratory F-term (reference) 2H025 AA01 AA02 AA03 AA09 AB08 AB16 AC05 AC06 AD03 BE00 BE10 BG00 CB08 CB10 CB14 CB16 CB41 CB45 CC03 CC20 FA12 4J002 BC131 BG071 BH011 BK001 DF007 EH008 EJ038 EJ058 EJ068 EN047 EN097 EU0 EN047 EN037 EN077 EN047 EW176 GP03 4J100 AB07P AB07Q AB07R AL03Q AL08Q AM47Q BA02Q BA03P BA20Q BA22R BC03Q BC09Q CA04 CA05 FA03 FA19 JA38

Claims (7)

[Claims] 1. It has a repeating unit containing a naphthalene ring having a hydroxy group represented by the following general formula (1) and a repeating unit having a group in which a hydrogen atom of a hydroxyl group of a carboxyl group is substituted by an acid labile group. A resist material comprising a polymer. Embedded image (In the formula, R ¹ is a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and a is an integer of 1 to 5. ) 2. The polymer according to claim 1, wherein the repeating unit having a group in which a hydrogen atom of a hydroxyl group of a carboxyl group is substituted by an acid labile group has the following general formula (2) -1 to (2): -4. Embedded image (Wherein, R ² represents a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and R ³ represents an acid labile group. b is 0 or 1, X and Y are a single bond or a linear, branched or cyclic divalent hydrocarbon group having 1 to 10 carbon atoms;
The group may include a hydroxy, acetyl or ester group. Z is an oxygen atom or a -NR- group (R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms). ) 3. The resist material according to claim 1, wherein the polymer further contains a repeating unit represented by the following general formula (1 ′). Embedded image (In the formula, R ¹ , R ³ and a have the same meanings as described above.) 4. The polymer according to claim 1, wherein the base resin is alkali-insoluble or hardly soluble, and becomes alkali-soluble when the acid labile group is eliminated. A chemically amplified positive resist material for electron beam, X-ray, or soft X-ray exposure, comprising (B) an organic solvent and (C) an acid generator. 5. The electron beam, X-ray or soft X-ray according to claim 4, further comprising (D) a basic compound.
Chemically amplified positive resist material for line exposure. 6. The chemically amplified positive resist composition for electron beam, X-ray or soft X-ray exposure according to claim 4, further comprising (E) a dissolution inhibitor. 7. A step of (1) applying the chemically amplified positive resist material according to any one of claims 4, 5, and 6 on a substrate; and (2) a step of applying a photomask after heat treatment. Exposing to an electron beam, X-ray, or soft X-ray having a wavelength of 300 nm or less through the process, and (3) performing a heat treatment as necessary and then developing using a developer. Pattern formation method.