JP2002072482A - Positive type photoresist composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a superior positive type photoresist composition which does not cause the problem of development defects when far UV, particularly KrF excimer laser light, is used as a light source for exposure. SOLUTION: The positive type photoresist composition contains (A) a compound which generates an acid when irradiated with active light or radiation, (B) an alkali-insoluble or slightly alkali-soluble resin made alkali-soluble by the action of the acid and (C) a specified carboxylic acid derivative having a molecular weight of <=1,000.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a lithographic printing plate or an IC.
The present invention relates to a positive photosensitive composition used in a semiconductor manufacturing process such as the above, a circuit substrate such as a liquid crystal and a thermal head, and other photofabrication processes.
In particular, the photoresist composition of the present invention acts by high-energy radiation such as deep ultraviolet rays (including excimer lasers), electron beams, X-rays, or emitted light, and is suitably used for the production of semiconductor integrated circuits. It is.

[0002]

2. Description of the Related Art Conventionally, in the process of manufacturing semiconductor devices such as ICs and LSIs, fine processing by lithography using a photoresist composition has been performed. 2. Description of the Related Art In recent years, with the increase in the degree of integration of integrated circuits, formation of ultrafine patterns in a submicron region or a quarter-micron region has been required. Accordingly, the exposure wavelength tends to be shortened from g-line to i-line and further to KrF excimer laser light. At present, lithography using excimer laser light is an important processing technique in this field, and a chemically amplified resist is adopted as a resist suitable for such an excimer laser lithography process.

A chemically amplified resist composition generates an acid in an exposed portion by irradiation with radiation such as deep ultraviolet light, and a reaction using the acid as a catalyst causes a reaction between a portion irradiated with active radiation and a portion not irradiated with a developing solution. A material that forms a pattern on a substrate by changing its solubility. The chemically amplified resist has high sensitivity and resolution, and has an advantage that an image can be formed with a compound capable of generating an acid by a small amount of radiation (hereinafter referred to as a photoacid generator).

As an example of a chemically amplified positive resist, a compound capable of generating an acid by photolysis, acetal or O, N
-Combination with acetal compound (JP-A-48-8900)
No. 3), a combination with an orthoester or amide acetal compound (JP-A-51-120714), a combination with a polymer having an acetal or ketal group in the main chain (JP-A-53-133429), and an enol ether compound. (Japanese Unexamined Patent Publication (Kokai) No. 55-1295) and a combination with an N-acylimino carbonate compound (Japanese Unexamined Patent Publication (Kokai) No. 55-1295).
No. 6236), a combination with a polymer having an orthoester group in the main chain (JP-A-56-17345), a combination with a tertiary alkyl ester compound (JP-A-60-362).
No. 5), a combination with a silyl ester compound (JP-A-60 / 1985)
-10247) and a combination with a silyl ether compound (JP-A-60-37549, JP-A-60-1214).
No. 46).

Similarly, systems which are stable under aging at room temperature, but are decomposed by heating in the presence of an acid and solubilized in alkali are disclosed in, for example, JP-A-59-45439, JP-A-60-3625, JP-A-62-229242, JP-A-63-27829, JP-A-63-36240, JP-A-63-250642, Polym. Eng. Sci., Vol. 23, 101
2 (1983); ACS.Sym. 242, 11 (1984); Semicond
uctor World 1987, November, p. 91; Macromolecules, 2
Vol. 1, p. 1475 (1988); SPIE, vol. 920, p. 42 (1988);
Combination systems with esters or carbonate compounds of primary or secondary carbons (eg t-butyl, 2-cyclohexenyl). Since these systems also have high sensitivity and low absorption in the far ultraviolet region, they can be effective systems for shortening the light source wavelength capable of ultrafine processing.

The positive chemically amplified resist is decomposed by the reaction of a three-component system comprising an alkali-soluble resin, a photoacid generator, and a compound having an acid-decomposable group and a dissolution inhibiting compound for the alkali-soluble resin, and decomposed by the reaction with an acid. A two-component system comprising a resin having a group that becomes soluble and a photoacid generator, and a resin having a group that becomes alkali-soluble by being decomposed by reaction with an acid;
It can be broadly classified into a hybrid system comprising a low molecular weight dissolution inhibiting compound having an acid-decomposable group and a photoacid generator. In these two-component, three-component and hybrid positive chemically amplified resists, an acid from a photoacid generator is interposed by exposure, and after heat treatment, development is performed to obtain a resist pattern.

In lithography using a chemically amplified resist, sensitivity, resolution, profile,
Coating properties, heat resistance, dry etching resistance, adhesion, substrate dependence, environmental stability (eg, resist dimensional stability due to fluctuations in withdrawal time), and depth of focus (eg, pattern formation against defocus during radiation irradiation) Photoresist excellent in various properties such as properties) has been demanded, and many ideas for improving the performance by additives have been disclosed.

Due to the specific reaction mechanism of the chemically amplified positive resist, attempts have been made to prevent the diffusibility of the generated acid by adding an acid scavenger to thereby improve the resist properties, especially the environmental stability. I have. For example, JP-A-5-12
No. 7369, No. 5-232706, No. 5-24966
No. 2, 5-289322, 6-317902,
As disclosed in, for example, JP-A-7-92678 and JP-A-7-120929, organic amines have been proposed. However, when an amine is added, there is a problem that the resolution is improved but the sensitivity is lowered. It is known to add an organic amine to a chemically amplified resist.

Further, Japanese Patent Application Laid-Open No. 10-20501 discloses a mono-carboxylic acid specific to a chemically amplified resist, that is, an alkyl carboxylic acid having 4 to 20 carbon atoms, for the purpose of improving resolution and resist pattern shape. And addition of fluoroalkyl carboxylic acids.

For the purpose of improving the resolution and stability of a chemically amplified resist, a compound containing an organic carboxylic acid and an amine is disclosed in Japanese Patent Application Laid-Open No. 9-6001. It has been known that a device for improving the storage stability with time between the PEBs is made. Also, addition of a surfactant such as a fluorine-based surfactant is disclosed in, for example, JP-A-7-92679 and is well known.

Further, there is disclosed a device for improving resist characteristics such as resolution, exposure latitude, adhesion, and substrate dependence. For example, JP-A-9-5987, U.S. Pat. No. 5,770,343, and EP-A-749044 disclose methods of preventing pattern collapse by adding formamide or acetamide compound.
No. 44950 discloses that the dependency on the substrate is improved by adding a nitrogen-containing compound such as succinimide or phthalimide. JP-A-5-232706,
No. 6-11835, No. 6-242606, No. 6-2
No. 66100, No. 7-333851, No. 7-3338
No. 44, U.S. Pat. No. 5,663,035, European Patent 6777
No. 88, a compound (photobase) whose basicity is reduced by exposure is added to provide environmental stability (for example,
There is disclosed a method for improving resist dimensional stability due to fluctuations in the withdrawal time, resolution, depth of focus, and the like.

Apart from the resist performance as described above, the occurrence of defects due to the lithography process is one of the major factors for lowering the yield, and has recently become a particularly important problem. For example, it is said that development defects are generally caused by bubbles at the time of liquid filling and microbubbles due to dissolved gas in the developer (Hirano et al .; Proceedings of the 42nd JSAP 27p-). ZW-9 (19
96)), as the diameter of the wafer increases and the discharge amount of the developer increases, it is more important to take measures against bubbles. As a countermeasure against these bubbles, improvement of the apparatus to discharge the developing solution softly (see Science Forum Publishing Co., Ltd., ULSI Manufacturing Contamination Control Technology, 41 (1992)) and addition of a degassing mechanism for dissolved gas to add bubbles Attempts have been made to reduce this, but not to a satisfactory level.

Further, in order to reduce development defects, a nonionic surfactant is added to the developer to improve the wettability of the developer and to promote bubble desorption.
Attempts have been made to improve the affinity by optimizing the type and amount of surfactant in a naphthoquinonediazide-based resist (Tasushima et al .; Proceedings of the 42nd JSAP 27p-ZW-7) (1996)).

However, in order to reduce development defects of the chemically amplified resist, these methods are not only insufficient, but may even have an adverse effect. There is no guideline for improvement at all. In addition, if the affinity of the resist is improved to reduce development defects, the residual film ratio and the profile tend to deteriorate, and it is extremely difficult to achieve both. However, when the amine is added to a two-component chemically amplified resist, it certainly has an effect on a change in profile and a change in line width, but results in inferior development defects, and a countermeasure is required.

Further, a strongly basic and low boiling point amine (for example, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine) and an aromatic carboxylic acid (for example, disclosed in JP-A-9-6001) are disclosed. Salicylic acid, nitrobenzoic acid,
When (phthalic acid) is added to the chemically amplified resist for KrF excimer laser, although the effect on the storage stability with time between exposure and PEB is seen, the development defects are extremely poor. Was desired. In addition, amines having a low boiling point have caused problems in processes such as contamination of equipment used for semiconductor production such as a hot plate with the amine.

[0016]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a positive photoresist composition which does not cause a problem of development defects when far ultraviolet rays, particularly KrF excimer laser light, are used as an exposure light source. It is in. Another object of the present invention is to provide a positive photoresist composition having excellent stability in a semiconductor manufacturing process.

[0017]

Means for Solving the Problems As a result of intensive studies on the constituent materials of a resist composition in a positive-type chemical amplification system, the present inventors have found that a resin containing an acid-decomposable group, a photoacid generator, and a specific acid The inventors have found that the object can be achieved by combining a carboxylic acid derivative having a partial structure and a molecular weight of 1,000 or less, thereby achieving the present invention.

That is, the present invention is an invention having the following constitutions (1) to (6) and achieves the above object. (1) (A) a compound which generates an acid upon irradiation with actinic rays or radiation, (B) a resin which is insoluble or hardly soluble in alkali and becomes alkali-soluble by the action of an acid, and (C) a general formula shown below A positive photoresist composition comprising a carboxylic acid derivative having a partial structure represented by (I) and having a molecular weight of 1,000 or less.

[0019]

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In the general formula (I), R ₁ represents a hydrogen atom, a fluorine atom, or —CF ₃ , and R ₂ represents a hydrogen atom, a fluorine atom, —CF ₃ , or —O—R ₃ . R
₃ represents an alkyl group having 1 to 4 carbon atoms or a fluoroalkyl group. m and n each independently represent an integer of 1 to 3. A plurality of R ₁ and a plurality of R ₂ may be the same or different. However, at least one of R ₁ and R ₂ of this structure represents a fluorine atom or a group containing a fluorine atom.

(2) The positive photoresist composition according to the above (1), wherein the carboxylic acid derivative (C) is a compound represented by the following general formula (II).

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(In the above formula (II), X is any one selected from a hydrogen atom, a fluorine atom, an alkyl group, a fluoroalkyl group, an alkoxy group and a fluoroalkoxy group. R ₁ , R ₂ , R ₃ , M, and n have the same meanings as in formula (I).) (3) The resin as the component (B) is represented by the following general formula (IV)
And the repeating unit represented by (V). (1) or (2).

[0023]

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(In the above formula, L represents a hydrogen atom, an optionally substituted linear, branched or cyclic alkyl group, or an optionally substituted aralkyl group. Z is a substituted or unsubstituted aralkyl group. Represents a linear, branched or cyclic alkyl group, or an optionally substituted aralkyl group.
Further, Z and L may combine to form a 5- or 6-membered ring. )

(4) The positive photoresist composition as described in any of (1) to (3) above, further comprising (D) a nitrogen-containing basic compound. (5) The positive photoresist composition as described in (4) above, wherein the nitrogen-containing basic compound contains at least one kind of aliphatic cyclic amine. (6) The above (1) to (E), further comprising (E) a fluorine-based and / or silicon-based surfactant.
The positive photoresist composition according to any of (5).

[0026]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the compounds used in the present invention will be described in detail. The component (C) used in the positive photoresist composition of the present invention, that is, a carboxylic acid derivative having a specific partial structure and having a molecular weight of 1,000 or less, is blended with the positive photoresist composition of the present invention to develop. Defects are significantly reduced.

The carboxylic acid derivative as the component (C) used in the present invention has a partial structure represented by the above general formula (I). Examples of the alkyl group for R ₃ include a methyl group, an ethyl group, a linear or branched propyl group, and a linear or branched butyl group. Further, as the fluoroalkyl group for R ₃ , one in which a hydrogen atom of an alkyl group having 1 to 4 carbon atoms is substituted with a fluorine atom, for example, -C
F ₃ and —CHF ₂ can be exemplified.

The (C) carboxylic acid derivative used in the present invention is preferably a compound represented by the above general formula (II). The alkyl group as X has 1 to 1 carbon atoms.
4 is preferable, and examples thereof include a methyl group, an ethyl group, a linear or branched propyl group, and a linear or branched butyl group. Fluoroalkyl group as X is preferably from 1 to 4 carbon atoms, which a hydrogen atom of the alkyl group are substituted with fluorine atoms, for example, a -CF _3. The alkoxy group as X can be from 1 to 4 carbon atoms include preferably, for example, C ₃ H ₇ O-a. or,
Fluoroalkoxy group as X can be from 1 to 4 carbon atoms include preferably, for example, C ₃ F ₇ O-a. X
Is a hydrogen atom, a fluorine atom, -CF _3, C ₃ fluoroalkyl group and a fluoroalkoxy group having 1 to 3 carbon atoms F ₇ O-are particularly preferred.

The molecular weight of the carboxylic acid derivative of the component (C) is 1,000 or less, preferably 100 to 800,
150-700 is more preferred. When the molecular weight exceeds 1,000, the above effects cannot be exhibited.

Examples of the carboxylic acid derivative as the component (C) used in the present invention include the following compounds.

[0031]

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[0032]

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(C) The carboxylic acid derivative having a specific partial structure and having a molecular weight of 1,000 or less according to the present invention can be used alone or in combination of two or more. Resist composition (solid content)
Usually, 0.01 to 15% by weight, preferably 0.1% by weight.
01 to 10% by weight. If the amount is less than 0.01% by weight, the effect of the present invention cannot be sufficiently obtained. If it exceeds 15% by weight, the residual film ratio tends to decrease. On the other hand, a low molecular weight aliphatic carboxylic acid, aromatic carboxylic acid or carboxylic anhydride other than the present invention may be mixed as long as the effects of the present invention are not impaired.

The photoacid generator (A) used in the present invention comprises:
A compound that generates an acid upon irradiation with actinic rays or radiation. As the photoacid generator used in the present invention, a photoinitiator for photocationic polymerization, a photoinitiator for photoradical polymerization, a photodecolorant for dyes, a photochromic agent, or a microresist is used. Known light (400 to 200 nm ultraviolet light, far ultraviolet light, particularly preferably g-line, h-line, i-line, K
rF excimer laser light), an ArF excimer laser light, an electron beam, an X-ray, a molecular beam or a compound capable of generating an acid by an ion beam, and a mixture thereof can be appropriately selected and used.

Other photoacid generators used in the present invention include, for example, onium salts such as diazonium salts, ammonium salts, phosphonium salts, iodonium salts, sulfonium salts, selenonium salts, arsonium salts, and the like.
Organic halogen compound, organic metal / organic halide, o
A photoacid generator having a nitrobenzyl-type protecting group; a compound represented by photolysis such as iminosulfonate which generates sulfonic acid; a disulfone compound; a diazoketosulfone; and a diazodisulfone compound.
Further, a group in which an acid is generated by such light or a compound in which a compound is introduced into a main chain or a side chain of a polymer can be used.

Further, VNRPillai, Synthesis, (1), 1 (198
0), A. Abad etal, Tetrahedron Lett., (47) 4555 (1971),
DHR Barton et al., J. Chem. Soc., (C), 329 (1970), U.S. Pat.No. 3,779,778, European Patent 126,712, etc. it can.

Among the above-mentioned photoacid generators, those which are used particularly effectively will be described below. (1) The following general formula (PAG) substituted with a trihalomethyl group
The oxazole derivative represented by 1) or the general formula (PA)
An S-triazine derivative represented by G2).

[0038]

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In the formula, R ²⁰¹ is a substituted or unsubstituted aryl group or alkenyl group, and R ²⁰² is a substituted or unsubstituted aryl group, alkenyl group, alkyl group, —C (Y) ₃
Show Y represents a chlorine atom or a bromine atom. Specific examples include the following compounds, but the present invention is not limited thereto.

[0040]

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(2) An iodonium salt represented by the following formula (PAG3) or a sulfonium salt represented by the following formula (PAG4).

[0042]

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Here, the formulas Ar ¹ and Ar ² each independently represent a substituted or unsubstituted aryl group. R ²⁰³ , R ²⁰⁴ , R
²⁰⁵ is each independently a substituted or unsubstituted alkyl group,
Indicates an aryl group.

[0044] Z ^- represents a counter anion, for example BF ₄ ^-,
_{AsF 6 -, PF 6 -,} SbF 6 -, SiF 6 2-, ClO 4 -,
CF ₃ SO ₃ ^- perfluoroalkane sulfonate anion such as an alkyl sulfonate anions such as camphorsulfonic acid anion, pentafluorobenzenesulfonic acid anion, benzenesulfonic acid anion, aromatic sulfonate anion such as triisopropyl benzenesulfonic acid anion And condensed polynuclear aromatic sulfonic acid anions such as naphthalene-1-sulfonic acid anion, anthraquinone sulfonic acid anion, sulfonic acid group-containing dyes, and the like, but are not limited thereto. Further, these anionic species may further have a substituent.

Further, two of R ²⁰³ , R ²⁰⁴ and R ²⁰⁵ and Ar ¹ and Ar ² may be bonded via a single bond or a substituent.

Specific examples include the following compounds, but are not limited thereto.

[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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[0052]

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[0053]

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The above onium salts represented by the general formulas (PAG3) and (PAG4) are known, for example, JWKnapczyk
etal, J. Am. Chem. Soc., 91, 145 (1969), AL Maycok
etal, J. Org. Chem., 35, 2532, (1970), E. Goethas etal,
Bull. Soc. Chem. Belg., 73,546, (1964), HMLeic
ester, J. Ame.Chem. Soc., 51,3587 (1929), JVC
rivello et al., J. Polym.Chem.Ed., 18,2677 (1980), U.S. Pat.Nos. 2,807,648 and 4,247,473, JP-A-53-10
It can be synthesized by the method described in 1,331 and the like.

(3) Disulfone derivatives represented by the following formula (PAG5) or iminosulfonate derivatives represented by the following formula (PAG6).

[0056]

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In the formula, Ar ³ and Ar ⁴ each independently represent a substituted or unsubstituted aryl group. R ²⁰⁶ represents a substituted or unsubstituted alkyl group or aryl group. A represents a substituted or unsubstituted alkylene group, alkenylene group, or arylene group. Specific examples include the following compounds, but are not limited thereto.

[0058]

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[0059]

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[0060]

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(4) A diazodisulfone derivative represented by the following general formula (PAG7).

[0062]

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Here, R represents a linear, branched or cyclic alkyl group or an optionally substituted aryl group. Specific examples include the following compounds, but are not limited thereto.

[0064]

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The amount of the photoacid generator to be added is generally in the range of 0.001 to 40% by weight, preferably 0.01 to 20% by weight, more preferably 0.01 to 20% by weight, based on the solid content in the composition. Is used in the range of 0.1 to 10% by weight.
When the addition amount of the photoacid generator is less than 0.001% by weight, the sensitivity is lowered. When the addition amount is more than 40% by weight, the light absorption of the resist becomes too high, the profile is deteriorated, and the process margin is reduced. It is not preferable because it becomes narrow.

The resin (B) used in the composition of the present invention, whose solubility in an alkali developing solution is increased by the action of an acid, has a repeating unit corresponding to hydroxystyrene, and is decomposed by the action of an acid to dissolve the alkali. Resins that increase solubility are preferably used.

Here, the hydroxystyrene includes o
It may be any of-, m-, or p-hydroxystyrene, and may be partially hydrogenated. Further, it may have a substituent other than a hydroxyl group. Examples of such a substituent include an alkyl group, an alkoxy group, an aralkyl group, and an aryl group.

The resin having a group which is decomposed by an acid and which increases the solubility in an alkali developing solution (also referred to as a group which can be decomposed by an acid) used in the positive chemically amplified resist of the present invention includes: It is a resin having an acid-decomposable group on the main chain or side chain, or on both the main chain and the side chain. Among them, a resin having a group which can be decomposed by an acid in a side chain is more preferable.

Preferred groups which can be decomposed by an acid are-
COOA ⁰ and —O—B ⁰ groups. Examples of the groups containing these include the groups represented by —R ⁰ —COOA ⁰ and —Ar—O—B ⁰ . Here, A ⁰ is -C (R ⁰¹ )
^{(R 02) (R 03)} , - showing the ^{Si (R 01) (R 02} ) (R 0 3) or ^{-C (R 04) (R 05} ) -O-R 06 group. B ⁰
Shows A ⁰ or -CO-O-A ⁰ group.

R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ and R ⁰⁵ are the same or different and each represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group, and R ⁰⁶ represents an alkyl group or an aryl group Is shown. However, R ^{01 to} R ⁰³
At least two are groups other than a hydrogen atom;
Two groups out of ^{01 to} R ⁰³ and R ^{04 to} R ⁰⁶ may combine to form a ring. R ⁰ represents an aliphatic or aromatic hydrocarbon group which may have a substituent, and -Ar- represents an aromatic group which may have a monocyclic or polycyclic substituent.

Here, the alkyl group is preferably an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group and a t-butyl group. Preferred are those having 3 to 10 carbon atoms such as cyclopropyl group, cyclobutyl group, cyclohexyl group and adamantyl group, and alkenyl groups having 2 to 2 carbon atoms such as vinyl group, propenyl group, allyl group and butenyl group. Preferably, the aryl group has 6 to 1 carbon atoms such as phenyl, xylyl, toluyl, cumenyl, naphthyl and anthracenyl.
Four are preferred.

These substituents include a hydroxyl group, a halogen atom (fluorine, chlorine, bromine, iodine), a nitro group, a cyano group, the above-mentioned alkyl group, methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, Hydroxypropoxy group, n-butoxy group, isobutoxy group, s
an alkoxy group such as an ec-butoxy group and a t-butoxy group,
Methoxycarbonyl group, alkoxycarbonyl group such as ethoxycarbonyl group, benzyl group, aralkyl group such as phenethyl group, cumyl group, aralkyloxy group, formyl group, acetyl group, butyryl group, benzoyl group, cyanyl group, acyl such as valeryl group Group, acyloxy group such as butyryloxy group, the above alkenyl group, vinyloxy group,
Examples thereof include an alkenyloxy group such as a propenyloxy group, an allyloxy group and a butenyloxy group, an aryloxy group such as the above-described aryl group and phenoxy group, and an aryloxycarbonyl group such as a benzoyloxy group.

The acid-decomposable group is preferably a silyl ether group, a cumyl ester group, an acetal group, a tetrahydropyranyl ether group, an enol ether group, an enol ester group, a tertiary alkyl ether group, or a tertiary alkyl ester. And tertiary alkyl carbonate groups. More preferred are a tertiary alkyl ester group, a tertiary alkyl carbonate group, a cumyl ester group, an acetal group, and a tetrahydropyranyl ether group. Particularly preferred is an acetal group.

Next, when the group decomposable by these acids is bonded as a side chain, the base resin has a repeating unit corresponding to the above-mentioned hydroxystyrene and has -OH or -COOH, preferably- It is an alkali-soluble resin having a ^R0- COOH or -Ar-OH group.
For example, an alkali-soluble resin described below can be used.

From the viewpoint of achieving a rectangular profile, an alkali-soluble resin having a high transmittance to far ultraviolet light or excimer laser light is preferable. Preferably, the transmittance at a wavelength of 248 nm with a thickness of 1 μm is 20 to 90%.

From these viewpoints, particularly preferred alkali-soluble resins are o-, m-, p-poly (hydroxystyrene) and copolymers thereof, hydrogenated poly (hydroxystyrene), halogen- or alkyl-substituted poly ( Hydroxystyrene), partially O-alkylated or O-acylated poly (hydroxystyrene), styrene-
A hydroxystyrene copolymer, an α-methylstyrene-hydroxystyrene copolymer and a hydrogenated novolak resin.

The resin having a group decomposable with an acid used in the present invention is disclosed in European Patent No. 254853, JP-A No. 2-25
No. 850, No. 3-223860, No. 4-251259
As described in No. 2, the alkali-soluble resin is reacted with a precursor of an acid-decomposable group, or an alkali-soluble resin monomer having an acid-decomposable group bonded thereto is copolymerized with various monomers. Can be obtained.

Specific examples of the resin (B) having a group capable of being decomposed by an acid used in the present invention are shown below, but the present invention is not limited thereto.

Pt-butoxystyrene / p-hydroxystyrene copolymer, p- (t-butoxycarbonyloxy) styrene / p-hydroxystyrene copolymer, p
-(T-butoxycarbonylmethyloxy) styrene /
p-hydroxystyrene copolymer, 4- (t-butoxycarbonylmethyloxy) -3-methylstyrene / 4
Hydroxy-3-methylstyrene copolymer, p- (t-
(Butoxycarbonylmethyloxy) styrene / p-hydroxystyrene (10% hydrogenated) copolymer, m-
(T-butoxycarbonylmethyloxy) styrene / m
-Hydroxystyrene copolymer, o- (t-butoxycarbonylmethyloxy) styrene / o-hydroxystyrene copolymer, p- (cumyloxycarbonylmethyloxy) styrene / p-hydroxystyrene copolymer,

P- (t-butoxycarbonylmethyloxy) styrene / p-hydroxystyrene / styrene copolymer, pt-butoxystyrene / p-hydroxystyrene / fumaronitrile copolymer, p-hydroxystyrene / t-butyl Methacrylate copolymer, styrene / p
-Hydroxystyrene / t-butyl methacrylate copolymer p-hydroxystyrene / t-butyl acrylate copolymer, styrene / p-hydroxystyrene / t-butyl acrylate copolymer p- (t-butoxycarbonylmethyloxy) styrene / p-hydroxystyrene /
N-methylmaleimide copolymer, p-hydroxystyrene / t-butyl acrylate / p-acetoxystyrene copolymer, p-hydroxystyrene / t-butyl acrylate / p- (t-butoxycarbonyloxy) styrene copolymer, p-hydroxystyrene / t-butyl acrylate / p- (t-butoxycarbonylmethyloxy) styrene copolymer,

[0081]

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In the present invention, as the resin having an acid-decomposable group (component (B)), a resin containing a repeating structural unit represented by the above general formula (IV) or (V) is preferable. Thereby, the effect of the present invention becomes more remarkable. Examples of the alkyl group of L and Z in the general formula (IV) include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, a pentyl group, a cyclopentyl group, and a hexyl group. , Cyclohexyl, octyl, dodecyl, etc.
Up to 20 linear, branched or cyclic ones can be mentioned.

Preferred substituents which the alkyl groups of L and Z may have include an alkyl group, an alkoxy group, a hydroxyl group,
Halogen atom, nitro group, acyl group, acyloxy group,
Acylamino group, a sulfonylamino group, an alkylthio group, an arylthio group, an aralkylthio group, a thiophenecarbonyloxy group, a thiophenemethylcarbonyloxy group, and a heterocyclic residue such as a pyrrolidone residue.
Preferably, it has 12 or less carbon atoms. As an alkyl group having a substituent, for example, cyclohexylethyl group, alkylcarbonyloxymethyl group, alkylcarbonyloxyethyl group, arylcarbonyloxyethyl group, aralkylcarbonyloxyethyl group, alkyloxymethyl group, aryloxymethyl group, aralkyloxymethyl Group, alkyloxyethyl group, aryloxyethyl group, aralkyloxyethyl group, alkylthiomethyl group, arylthiomethyl group, aralkylthiomethyl group,
Examples thereof include an alkylthioethyl group, an arylthioethyl group, and an aralkylthioethyl group. The alkyl in these groups is not particularly limited, but may be any of chain, cyclic, and branched, and may further have a substituent such as the above-described alkyl group and alkoxy group. Examples of the alkylcarbonyloxyethyl group include a cyclohexylcarbonyloxyethyl group, a t-butylcyclohexylcarbonyloxyethyl group, an n-butylcyclohexylcarbonyloxyethyl group, and the like. The aryl is not particularly limited, but is generally a phenyl group, a xylyl group,
Examples thereof include those having 6 to 14 carbon atoms such as a toluyl group, a cumenyl group, a naphthyl group, and an anthracenyl group, and may further have a substituent such as the above-described alkyl group and alkoxy group. Examples of the aryloxyethyl group include a phenyloxyethyl group and a cyclohexylphenyloxyethyl group. The aralkyl is not particularly limited, but examples thereof include a benzyl group. Examples of the aralkylcarbonyloxyethyl group include a benzylcarbonyloxyethyl group.

The aralkyl group of L and Z in the general formula (IV) includes, for example, a substituted or unsubstituted benzyl group,
Examples thereof include those having 7 to 15 carbon atoms such as a substituted or unsubstituted phenethyl group. Preferred substituents on the aralkyl group include an alkoxy group, a hydroxyl group, a halogen atom, a nitro group, an acyl group, an acylamino group, a sulfonylamino group, an alkylthio group, an arylthio group, an aralkylthio group, and the like. Examples thereof include an alkoxybenzyl group, a hydroxybenzyl group, and a phenylthiophenethyl group. The range of the carbon number of the substituent which the aralkyl group as L or Z may have is preferably 12 or less.

As described above, the introduction of a bulky group such as a phenyl group or a cyclohexyl group at the terminal of a substituted alkyl group or a substituted aralkyl group can further improve edge roughness.

5 or 6 formed by combining L and Z with each other
Examples of the member ring include a tetrahydropyran ring and a tetrahydrofuran ring.

The molar ratio of the repeating structural unit represented by the general formula (IV) to the repeating structural unit represented by the general formula (V) in the resin is preferably from 1/99 to 60/40, more preferably Is 5/95 to 50/50, more preferably 10/90 to 40/60.

The resin containing the repeating structural units represented by the general formulas (IV) and (V) may contain structural units derived from other monomers.

Other monomers include hydrogenated hydroxystyrene; halogen, alkoxy or alkyl-substituted hydroxystyrene; styrene; halogen, alkoxy, acyloxy or alkyl-substituted styrene; maleic anhydride; acrylic acid derivative; methacrylic acid derivative;
-Substituted maleimide and the like, but are not limited thereto.

The ratio between the structural units of the general formulas (IV) and (V) and the structural units of the other monomers is represented by the following molar ratio:
[(IV) + (V)] / [other monomer components] = 100
/ 0 to 50/50, preferably 100/0 to 60/4
0, more preferably 100/0 to 70/30.

Specific examples of the resin containing a repeating structural unit represented by the above general formulas (IV) and (V) include:
The following are mentioned.

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[0101]

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In the above specific examples, Me is a methyl group, E
t represents an ethyl group, nBu represents an n-butyl group, iso-Bu represents an isobutyl group, and tBu represents a t-butyl group.

When an acetal group is used as the acid-decomposable group, a polyhydroxy compound is added in the synthesis stage to adjust the alkali dissolution rate and improve heat resistance to introduce a cross-linking site connecting the polymer main chain with a polyfunctional acetal group. May be. The amount of the polyhydroxy compound to be added is 0.01 to 5 mol%, more preferably 0.05 to 4 mol%, based on the amount of hydroxyl groups of the resin.

Examples of the polyhydroxy compound include those having 2 to 6 phenolic hydroxyl groups or alcoholic hydroxyl groups, preferably 2 to 4 hydroxyl groups, and more preferably 2 or 3 hydroxyl groups. Individual. Specific examples of the polyhydroxy compound are shown below, but the present invention is not limited thereto.

[0105]

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In the present invention, the content of the repeating unit having an acid-decomposable group in the resin (B) is preferably from 5 to 50 mol%, more preferably from 10 to 40 mol%, based on all repeating units. It is.

In the present invention, the content of the repeating unit corresponding to hydroxystyrene in the resin (B) is preferably from 5 to 95 mol%, more preferably from 10 to 85 mol%, based on all repeating units. is there.

The weight average molecular weight (Mw) of the resin having an acid-decomposable group is preferably in the range of 2,000 to 300,000. If it is less than 2,000, the film thickness is greatly reduced due to the development of the unexposed portion. Here, the weight average molecular weight is defined as a polystyrene equivalent value of gel permeation chromatography.

The degree of dispersion (weight average molecular weight / number average molecular weight) of the resin having an acid-decomposable group is 1.0 to 5.0.
Is preferable. If the degree of dispersion is more than 5.0, the resolving power is lowered and the resist pattern becomes tapered, which is not preferable.

The component (B) of the photosensitive composition of the present invention, that is, a resin having an acid-decomposable group, may be used as a mixture of two or more kinds. Component (B) is used in an amount of 40 to 9 based on the total weight of the photosensitive composition (excluding the solvent).
It is 9% by weight, preferably 60 to 98% by weight.

Next, the nitrogen-containing basic compound (D) preferably used in the positive photoresist composition of the present invention will be described. As the nitrogen-containing basic compound, an organic amine, a basic ammonium salt, a sulfonium salt, or the like is used, and any compound that does not deteriorate sublimation or resist performance may be used.A preferable nitrogen-containing basic compound is more basic than phenol. Is a strong compound. By using the nitrogen-containing basic compound, the change in performance over time from exposure to post-heating can be reduced, and development defects can be reduced by the effect of the combination with the carboxylic anhydride. A nitrogen-containing basic compound having the following structure is preferably used.

[0112]

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Here, R ²⁵⁰ , R ²⁵¹ and R ²⁵² are the same or different and are a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aminoalkyl group having 1 to 6 carbon atoms, a hydroxyalkyl having 1 to 6 carbon atoms. Or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, wherein R ²⁵¹ and R ²⁵² may be bonded to each other to form a ring.

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Wherein R ²⁵³ , R ²⁵⁴ , R ²⁵⁵ and R ²⁵⁶
Are the same or different and represent an alkyl group having 1 to 6 carbon atoms)

Further preferred compounds are nitrogen-containing cyclic compounds or two nitrogen atoms having different chemical environments in one molecule.
It is a nitrogen-containing basic compound having at least one compound. The nitrogen-containing cyclic compound more preferably has a polycyclic structure.
As the nitrogen-containing polycyclic compound, an aliphatic cyclic amine is preferable, and specific examples include a compound represented by the following general formula (VI).

[0117]

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In the formula (VI), Y and W each independently represent a linear, branched or cyclic alkylene group which may contain a hetero atom and may be substituted. Here, examples of the hetero atom include a nitrogen atom, a sulfur atom, and an oxygen atom. The alkylene group preferably has 2 to 10 carbon atoms, and more preferably has 2 to 5 carbon atoms. Examples of the substituent of the alkylene group include an alkyl group having 1 to 6 carbon atoms, an aryl group, an alkenyl group, a halogen atom, and a halogen-substituted alkyl group. Further, specific examples of the compound represented by the general formula (VI) include the following compounds.

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Of the above, 1,8-diazabicyclo [5.4.0] undec-7-ene and 1,5-diazabicyclo [4.3.0] non-5-ene are particularly preferred.

The nitrogen-containing basic compound having two or more nitrogen atoms having different chemical environments in one molecule is particularly preferably a compound containing both a substituted or unsubstituted amino group and a ring structure containing a nitrogen atom. Or a compound having an alkylamino group.

Preferred examples include substituted or unsubstituted guanidine, substituted or unsubstituted aminopyridine, substituted or unsubstituted aminoalkylpyridine, substituted or unsubstituted aminopyrrolidine, substituted or unsubstituted indazole, substituted or unsubstituted indazole, Unsubstituted pyrazole, substituted or unsubstituted pyrazine, substituted or unsubstituted pyrimidine, substituted or unsubstituted purine, substituted or unsubstituted imidazoline, substituted or unsubstituted pyrazoline, substituted or unsubstituted piperazine, substituted or unsubstituted Substituted aminomorpholine, substituted or unsubstituted aminoalkylmorpholine and the like can be mentioned. Preferred substituents are an amino group, aminoalkyl group, alkylamino group, aminoaryl group, arylamino group, alkyl group, alkoxy group, acyl group, acyloxy group, aryl group, aryloxy group, nitro group, hydroxyl group, cyano group It is.

Particularly preferred compounds are guanidine and
1,1-dimethylguanidine, 1,1,3,3-tetramethylguanidine, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-dimethylaminopyridine, 4-dimethylaminopyridine, 2-diethylamino Pyridine, 2- (aminomethyl) pyridine, 2-amino-3-methylpyridine, 2-amino-4-methylpyridine, 2-amino-5-methylpyridine, 2-amino-6-methylpyridine, 3-aminoethyl Pyridine, 4
-Aminoethylpyridine, 3-aminopyrrolidine, piperazine, N- (2-aminoethyl) piperazine, N-
(2-aminoethyl) piperidine, 4-amino-2,
2,6,6-tetramethylpiperidine, 4-piperidinopiperidine, 2-iminopiperidine, 1- (2-aminoethyl) pyrrolidine, pyrazole, 3-amino-5-methylpyrazole, 5-amino-3-methyl -1-p-tolylpyrazole, pyrazine, 2- (aminomethyl) -5
-Methylpyrazine, pyrimidine, 2,4-diaminopyrimidine, 4,6-dihydroxypyrimidine, 2-pyrazoline, 3-pyrazoline, N-aminomorpholine, N-
(2-Aminoethyl) morpholine, trimethylimidazole, triphenylimidazole, methyldiphenylimidazole, and the like, but are not limited thereto.

The nitrogen-containing basic compounds used in the present invention can be used alone or in combination of two or more. The amount of the nitrogen-containing basic compound used is usually 0.001 to 10% by weight, based on the solid content of the photosensitive composition,
Preferably it is 0.01 to 5% by weight. If the amount is less than 0.001% by weight, the effect of adding the nitrogen-containing basic compound cannot be obtained. On the other hand, if it exceeds 10% by weight, sensitivity tends to decrease and developability of unexposed areas tends to deteriorate.

Next, the fluorine-based surfactant and the silicon-based surfactant contained in the positive photoresist composition of the present invention will be described. The positive photoresist composition of the present invention can contain either or both of a fluorine-based surfactant and a silicon-based surfactant.

As these surfactants (E), for example, JP-A-62-36663, JP-A-61-226746, JP-A-61-2267
No. 45, JP-A-62-170950, JP-A-63-34540, JP-A-7
-230165, JP-A-8-62834, JP-A-9-54432, JP-A-9-5988, U.S. Patent 5,405,720, U.S. Patent 5,360,692,
U.S. Pat.No. 5,529,881, U.S. Pat.No. 5,296,330, U.S. Pat.
No. 098, US Pat. No. 5,576,143, US Pat. No. 5,296,143, US Pat. No. 5,294,511, and US Pat. No. 5,824,451. The following commercially available surfactants can be used as they are. As commercially available surfactants that can be used, for example, F-top EF301, EF303, (Shin-Akita Kasei
Co., Ltd.), Florado FC430, 431 (Sumitomo 3M Limited)
), Megafac F171, F173, F176, F189, R08 (Dai Nippon Ink Co., Ltd.), Surflon S-382, SC101, 102,
103, 104, 105, 106 (manufactured by Asahi Glass Co., Ltd.), Troysol S
-366 (manufactured by Troy Chemical Co., Ltd.) or a silicon-based surfactant.
Also, polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can be used as a silicon-based surfactant. Among these surfactants, surfactants having both fluorine atoms and silicon atoms are particularly excellent in terms of improvement of development defects.

The amount of the surfactant (E) is usually from 0.01% by weight to 2% by weight, preferably from 0.01% by weight to 1% by weight, based on the solids in the composition of the present invention. These surfactants can be used alone or in combination of two or more.

The positive photoresist composition of the present invention comprises
It is not well understood why it is specifically superior to the development defects described above, but (C) a carboxylic acid derivative having a specific partial structure and a molecular weight of 1000 or less is blended, and preferably (D) is further added. It is thought that this was caused by combining a nitrogen basic compound and (E) a fluorine-based and / or silicon-based surfactant.

The positive photoresist composition of the present invention comprises
After being dissolved in a solvent that dissolves each of the above components, the solution is usually adjusted, for example, by filtration through a filter having a pore size of about 0.05 μm to 0.2 μm to prepare a solution.

Examples of the solvent used herein include ethylene glycol monoethyl ether acetate, cyclohexanone, 2-heptanone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, and propylene glycol monoethyl ether. Acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl β-methoxyisobutyrate, ethyl butyrate, propyl butyrate, methyl isobutyl ketone, ethyl acetate, isoamyl acetate, ethyl lactate, toluene, xylene, cyclohexyl acetate, diacetone Alcohol, N-methylpyrrolidone, N, N-dimethylformamide, γ-butyrolactone, N, N-dimethylacetamide , Propylene carbonate, ethylene carbonate and the like.

These solvents are used alone or in combination. The choice of solvent is important because it affects the solubility in the positive photoresist composition of the present invention, the applicability to a substrate, the storage stability, and the like. It is preferable that the amount of water contained in the solvent be small because it affects various resist properties.

Further, in the positive photoresist composition of the present invention, it is preferable to reduce metal impurities such as metals and impurity components such as chloride ions to 100 ppb or less. The presence of many of these impurities is not preferable because it causes operation failure, defects, and reduced yield in manufacturing a semiconductor device.

The solid content of the positive photoresist composition is preferably dissolved in the above solvent and dissolved in a solid concentration of 3 to 40%. More preferably, it is 5 to 30%, and still more preferably 7 to 20%.

The positive resist composition of the present invention may further contain an acid-decomposable dissolution inhibiting compound, a dye, a plasticizer,
Photosensitizer, organic basic compound, crosslinking agent, photobase generator,
A thermal base generator, a spectral sensitizer, a compound that promotes solubility in a developer, and the like can be contained.

Examples of the acid-decomposable dissolution inhibiting compound which can be used in the positive photoresist composition of the present invention include low-molecular acid-decomposable dissolution inhibiting compounds described in JP-A-5-134415 and JP-A-6-51519. Compounds can be used.

Examples of the plasticizer that can be used in the positive photoresist composition of the present invention include JP-A-4-212960,
JP-A-8-262720, EP 735422,
Compounds described in EP 416873, EP 439371 and U.S. Pat. No. 5,846,690, specifically, di (2-ethylhexyl) adipate, n-hexyl benzoate, di-n-octyl phthalate, di-n-phthalate -Butyl, benzyl phthalate-n-butyl, dihydroabiethyl phthalate and the like.

As the compound which can be used in the present invention and which promotes solubility in a developer, for example, JP-A No. 4-13 / 1990
No. 4345, JP-A-4-217251, JP-A-7-1
No. 81680, Japanese Patent Application Laid-Open No. Hei 8-21597, U.S. Pat.
And polyhydroxy compounds described in JP-A Nos. 688628 and 5972559. Examples thereof include 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4- (α-methylbenzylidene) bisphenol and α, α ′, α ″ -tris. (4-hydroxyphenyl) -1,3,5-triisopropylbenzene, α, α ′, α ″ -tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene, 1,2,2-tris ( Hydroxyphenyl) propane, 1,1,2-tris (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2,5,5-tetrakis (4-hydroxyphenyl) hexane, 1,2-tetrakis (4 -Hydroxyphenyl) ethane, 1,1,3
Tris (hydroxyphenyl) butane, para [α,
Aromatic polyhydroxy compounds such as α, α ′, α′-tetrakis (4-hydroxyphenyl)]-xylene are preferably used.

Organic acids such as salicylic acid, diphenolic acid and phenolphthalein can also be used in combination with the acid anhydride of the present invention.
In Nos. 1263 and 7-92680, sulfonamide compounds and alkali-soluble resins such as polyhydroxystyrene resins described in JP-A-11-153869 can also be used in combination.

Suitable dyes that can be used in the present invention include oil dyes and basic dyes. Specifically, Oil Yellow # 101, Oil Yellow # 103, Oil Pink #
312, oil green BG, oil blue BOS, oil blue # 603, oil black BY, oil black BS, oil black T-505 (all manufactured by Orient Chemical Industry Co., Ltd.), crystal violet (CI
42555), methyl violet (CI4253)
5), rhodamine B (CI45170B), malachite green (CI42000), methylene blue (CI5
2015).

Further, the composition of the present invention contains JP-A-7-2
8247, EP 616258, U.S. Pat.
5443, JP-A-9-127700, European Patent 76
No. 2,207, U.S. Pat. No. 5,783,354, specifically, tetramethylammonium hydroxide, tetra-n-butylammonium hydroxide, betaine and the like can be added.
No. 6, No. 6-11835, No. 6-242606, No. 6-266100, No. 7-338381, No. 7-3
No. 33844, US Pat. No. 5,663,035, European Patent No. 6
A compound (photobase) whose basicity is reduced by exposure described in 77788 can also be added.

Further, a spectral sensitizer as described below is added to sensitize the photosensitive composition of the present invention to a longer wavelength region than far ultraviolet where the photoacid generator used has no absorption. Sensitivity can be given to i or g rays. Suitable spectral sensitizers include, specifically, benzophenone, p,
p'-tetramethyldiaminobenzophenone, p, p '
-Tetraethylethylaminobenzophenone, 2-chlorothioxanthone, anthrone, 9-ethoxyanthracene, anthracene, pyrene, perylene, phenothiazine, benzyl, acridine orange, benzoflavin,
Cetoflavin-T, 9,10-diphenylanthracene, 9-fluorenone, acetophenone, phenanthrene, 2-nitrofluorene, 5-nitroacenaphthene,
Benzoquinone, 2-chloro-4-nitroaniline, N-
Acetyl-p-nitroaniline, p-nitroaniline,
N-acetyl-4-nitro-1-naphthylamine, picramide, anthraquinone, 2-ethylanthraquinone,
2-tert-butylanthraquinone 1,2-benzanthraquinone, 3-methyl-1,3-diaza-1,9-benzanthrone, dibenzalacetone, 1,2-naphthoquinone, 3,3′-carbonyl-bis (5,7-dimethoxycarbonylcoumarin) and coronene, but are not limited thereto. Further, these spectral sensitizers can also be used as a light absorbing agent for far ultraviolet light of a light source.
In this case, the light absorbing agent can reduce the reflected light from the substrate and reduce the effect of multiple reflection in the resist film, thereby reducing the standing wave.

Examples of the photobase generator which can be added to the composition of the present invention include JP-A-4-151156 and JP-A-4-1620.
No. 40, No. 5-197148, No. 5-5995, No. 6
No. 194834, No. 8-146608, No. 10-8
No. 3079 and EP 622682. Specific examples thereof include 2-nitrobenzyl carbamate, 2,5-dinitrobenzylcyclohexyl carbamate, N-cyclohexyl-4-methylphenylsulfonamide, and 1,1- Dimethyl-2-phenylethyl-N
-Isopropyl carbamate and the like can be suitably used. These photobase generators are added for the purpose of improving the resist shape and the like.

Examples of the thermal base generator include, for example, those described in
Nos. 158242 and 158239, U.S. Pat.
No. 143 can be mentioned.

Such a positive photoresist composition of the present invention is applied on a substrate to form a thin film. The thickness of this coating film is preferably from 0.2 to 4.0 μm. In the present invention, if necessary, a commercially available inorganic or organic antireflection film can be used. Further, an antireflection film can be applied to the upper layer of the resist and used.

The antireflection film used as the lower layer of the resist may be any of an inorganic film type such as titanium, titanium dioxide, titanium nitride, chromium oxide, carbon and amorphous silicon, and an organic film type comprising a light absorbing agent and a polymer material. Can be used. The former is a vacuum evaporation system for film formation, C
Equipment such as VD equipment and sputtering equipment is required.

As the organic antireflection film, for example,
-Condensation product of a diphenylamine derivative and a formaldehyde-modified melamine resin described in -69611, an alkali-soluble resin, a light absorbing agent, and US Pat. No. 5,294,680.
Reaction product of a maleic anhydride copolymer and a diamine type light absorbing agent described in JP-A-6-118631, one containing a resin binder and a methylolmelamine-based thermal crosslinking agent, and a carboxylic acid group and epoxy described in JP-A-6-118656. Acrylic resin type antireflection film having a group and a light absorbing group in the same molecule,
Japanese Patent Application Laid-Open No. 8-17915, comprising a methylolmelamine and a benzophenone-based light-absorbing agent.
No. 09 obtained by adding a low-molecular light absorbing agent to the polyvinyl alcohol resin. As an organic antireflection film, DUV30 series and DUV-40 series manufactured by Brewer Science, and AR-
2. Commercially available organic anti-reflection films such as AR-3 and AR-5 can also be used.

The resist solution is coated on a substrate (eg, silicon / silicon dioxide coating) used for manufacturing precision integrated circuit devices (on a substrate provided with the antireflection film if necessary), a spinner, a coater, and the like. After coating by an appropriate coating method such as that described above, exposure through a predetermined mask, baking and development can provide a good resist pattern. Here, the exposure light is preferably 150
It is light having a wavelength of nm to 250 nm. Specifically, Kr
F excimer laser (248 nm), ArF excimer laser (193 nm), F ₂ excimer laser (157
nm), X-rays, electron beams and the like. In the present invention, an apparatus using a KrF excimer laser as an exposure light source is particularly preferably used.

Examples of the developer used in the composition of the present invention include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine and the like. Primary amines, diethylamine, di-n-
Secondary amines such as butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcoholamines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylhydroxyethylammonium hydroxide and the like And quaternary ammonium salts, and alkaline aqueous solutions of cyclic amines such as pyrrole and pyrhelidine. Further, an appropriate amount of an alcohol or a surfactant may be added to the above alkaline aqueous solution. A commercially available developer to which a surfactant is added, for example, HP manufactured by Fuji Film Ohlin Co., Ltd.
RD-402, -402Z or the like can be used.

Further, an appropriate amount of an anionic surfactant, a cationic surfactant, an antifoaming agent or the like can be used. These additives may be used to improve the performance of the resist, increase the adhesion to the substrate, reduce the amount of developer used, or reduce defects caused by bubbles during development. Added to the aqueous solution.

[0150]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples.

[Synthesis of Resin] Resin can be synthesized by acetalization using either a method using vinyl ether or an acetal exchange method using alcohol and alkyl vinyl ether. Further, for efficient and stable synthesis, a dehydration azeotropic method as described below can be used. However, it is not limited to these synthesis methods.

Synthesis Example 1 (Resin R-1) 32.4 g (0.2 mol) of p-acetoxystyrene was dissolved in 120 ml of butyl acetate, and dissolved in a stream of nitrogen and stirred.
At 0 ° C., azobisisobutyronitrile (AIBN)
033 g was added three times every 2.5 hours, and finally another 5
The polymerization reaction was performed by continuing stirring for a time. The reaction solution was poured into 1200 ml of hexane to precipitate a white resin. After drying the obtained resin, methanol 150 ml
Was dissolved. 7.7 g of sodium hydroxide (0.1 g
(9 mol) / water (50 ml) was added, and the mixture was heated under reflux for 3 hours for hydrolysis. After that, 200m of water
The mixture was diluted with 1 and neutralized with hydrochloric acid to precipitate a white resin. This resin was separated by filtration, washed with water and dried. Further, it was dissolved in 200 ml of tetrahydrofuran, and dropped and reprecipitated in 5 L of ultrapure water with vigorous stirring. This reprecipitation operation was repeated three times. The obtained resin is dried in a vacuum dryer for 12 hours.
After drying at 0 ° C. for 12 hours, an alkali-soluble poly (p-hydroxystyrene) resin R-1 was obtained. The weight average molecular weight of the obtained resin was 12,000.

Synthesis Example 2 (Resin R-2) 35.25 g (0.2 mol) of a p-tert-butoxystyrene monomer and 5.21 g (0.2 mol) of a t-Bu styrene monomer dehydrated and purified by a conventional method. .05 mol)
Was dissolved in 100 ml of tetrahydrofuran. Under a nitrogen stream and stirring, at 80 ° C., 0.033 g of azobisisobutyronitrile (AIBN) was added three times every 2.5 hours, and finally, stirring was continued for another 5 hours to carry out a polymerization reaction. . The reaction solution was poured into 1200 ml of hexane,
A white resin precipitated. After drying the obtained resin, it was dissolved in 150 ml of tetrahydrofuran. 4N hydrochloric acid was added thereto, and the mixture was hydrolyzed by heating under reflux for 6 hours, and then reprecipitated in 5 L of ultrapure water. The resin was separated by filtration, washed with water and dried. Further, it was dissolved in 200 ml of tetrahydrofuran, and dropped and reprecipitated in 5 L of ultrapure water with vigorous stirring. This reprecipitation operation was repeated three times. The obtained resin was dried in a vacuum dryer at 120 ° C. for 12 hours to obtain a poly (p-hydroxystyrene / t-butylstyrene) copolymer alkali-soluble resin R-2. The weight average molecular weight of the obtained resin was 12,000.

Synthesis Example-3 (Resin R-3) Poly (p-hydroxystyrene) manufactured by Nippon Soda Co., Ltd.
(VP8000) was designated as alkali-soluble resin R-3.
The weight average molecular weight was 9,800.

Synthesis Example-4 (Resin R-4) Poly (p-hydroxystyrene) manufactured by Nippon Soda Co., Ltd.
(VP15000) was designated as alkali-soluble resin R-4. The weight average molecular weight was 17000.

[Synthesis Example-5] 20 g of the alkali-soluble resin R-2 obtained in the above Synthesis Example 320 g of propylene glycol monomethyl ether acetate (PGMEA) was dissolved in a flask, and distilled under reduced pressure to obtain water and PGME.
A was distilled off azeotropically. After confirming that the water content was sufficiently low, 24 g of ethyl vinyl ether and 0.35 g of p-toluenesulfonic acid were added, and the mixture was stirred at room temperature for 1 hour.
Thereto was added 0.28 g of triethylamine to terminate the reaction. Ethyl acetate was added to the reaction solution, and after further washing with water, ethyl acetate, water and an azeotropic PGMEA were distilled off under reduced pressure to obtain a resin B protected with an acid-decomposable group according to the present invention.
-1 was obtained.

[Synthesis Example-6] 70 g of the alkali-soluble resin R-3 obtained in the above Synthesis Example 320 g of PGMEA was dissolved in a flask, and distilled under reduced pressure to obtain water and PGME.
A was distilled off azeotropically. After confirming that the water content was sufficiently low, 28 g of benzyl alcohol, 26 g of t-butyl vinyl ether and 0.35 g of p-toluenesulfonic acid were added, and the mixture was stirred at room temperature for 1 hour. After adding 0.1 g of triethylamine and stirring at room temperature for 10 minutes to terminate the reaction, ethyl acetate was added to the reaction solution, followed by washing with water, followed by distillation under reduced pressure to remove ethyl acetate, water and an azeotropic PGMEA. Is removed, and the resin B protected with an acid-decomposable group according to the present invention is removed.
-2 was obtained.

[Synthesis Example-7] 70 g of the alkali-soluble resin R-2 obtained in the above Synthesis Example 320 g of PGMEA was dissolved in a flask, and distilled under reduced pressure to obtain water and PGME.
A was distilled off azeotropically. After confirming that the water content was sufficiently low, 20 g of cyclohexylethanol, 15.5 g of t-butyl vinyl ether and 0.1 g of p-toluenesulfonic acid were added.
35 g was added, and the mixture was stirred at room temperature for 1 hour. After adding 0.28 g of triethylamine and stirring at room temperature for 10 minutes to terminate the reaction, ethyl acetate was added to the reaction solution, followed by washing with water, followed by distillation under reduced pressure to remove ethyl acetate, water and an azeotropic PGMEA. Was distilled off to obtain a resin B-3 protected by an acid-decomposable group according to the present invention.

[Synthesis Example-8] 70 g of the alkali-soluble resin R-3 obtained in the above Synthesis Example 320 g of PGMEA was dissolved in a flask, and distilled under reduced pressure to obtain water and PGME.
A was distilled off azeotropically. After confirming that the water content was sufficiently low, 22 g of cyclohexylethanol, 17.5 g of t-butyl vinyl ether and 0.1 g of p-toluenesulfonic acid were added.
35 g was added, and the mixture was stirred at room temperature for 1 hour. After adding 0.28 g of triethylamine and stirring at room temperature for 10 minutes to terminate the reaction, ethyl acetate was added to the reaction solution, followed by washing with water, followed by distillation under reduced pressure to remove ethyl acetate, water and an azeotropic PGMEA. Was distilled off to obtain a resin B-4 protected by an acid-decomposable group according to the present invention.

[Synthesis Example-9] 20 g of the alkali-soluble resin R-4 obtained in the above Synthesis Example 320 g of PGMEA was dissolved in a flask, and distilled under reduced pressure to obtain water and PGME.
A was distilled off azeotropically. After confirming that the water content was sufficiently low, 22.4 g of cyclohexylethanol, 17.5 g of t-butyl vinyl ether and 0.35 g of p-toluenesulfonic acid were added, and the mixture was stirred at room temperature for 1 hour. Then 5.5 g of pyridine and 5.9 g of acetic anhydride were added thereto, and the mixture was stirred at room temperature for 1 hour. Ethyl acetate was added to the reaction solution, and after further washing with water, ethyl acetate, water and an azeotropic PGMEA were distilled off under reduced pressure to obtain a resin B-5 protected by an acid-decomposable group according to the present invention. Was.

[Synthesis Example-10] 20 g of the alkali-soluble resin R-1 obtained in the above Synthesis Example 320 g of PGMEA was dissolved in a flask, and distilled under reduced pressure to obtain water and PGME.
A was distilled off azeotropically. After confirming that the water content was sufficiently low, 22.4 g of cyclohexylethanol, 17.5 g of t-butyl vinyl ether and 0.35 g of p-toluenesulfonic acid were added, and the mixture was stirred at room temperature for 1 hour. Then 5.5 g of pyridine and 5.9 g of acetic anhydride were added thereto, and the mixture was stirred at room temperature for 1 hour. Ethyl acetate was added to the reaction solution, and after further washing with water, ethyl acetate, water, and an azeotropic PGMEA were distilled off under reduced pressure to obtain a resin B-6 protected by an acid-decomposable group according to the present invention. Was.

[Preparation and Evaluation of Positive Photoresist Composition] A photosensitive resin composition having the following composition was mixed so as to have a solid content of about 12% by weight, and filtered with a 0.1 μm microfilter. A positive photoresist solution was prepared. That is, the resin synthesized in Synthesis Examples 5 to 10 and the following (A-
1) Photoacid generators represented by (A-3), the following (C-
1) to (C-8), the carboxylic acid derivatives of the present invention, the following nitrogen-containing basic compounds (D-1) to (D-3), and the following (W-1) to (W) Each component of the surfactant represented by -4) and the solvent represented by the following (S-1) to (S-4) was used.

For the positive photoresist composition thus prepared, the number of development defects was measured by the following method. Table 1 shows the measurement results of the number of development defects. [Evaluation Method of Development Defects] (1) Number of Development Defects-I The obtained positive photoresist solution was applied on a 6-inch silicon wafer by using a spin coater (Mark 8 manufactured by Tokyo Electron Limited), and was applied at 120 ° C. For 90 seconds using a vacuum adsorption type hot plate to form a resist film having a thickness of about 0.4 μm. And a KrF excimer laser (canon FPA with a wavelength of 248 nm and NA = 0.63)
-3000EX5). 10 after exposure
Heat treatment at 0 ° C. for 90 seconds, immediately develop with 2.38% tetramethylammonium hydroxide aqueous solution,
Subsequently, after rinsing with pure water, spin drying was performed to obtain a resist pattern. The number of development defects of the sample on which the contact hole pattern was formed was measured using a KLA2112 machine (manufactured by KLA Tencor Co., Ltd.) (Threshold 12, Pixel Size = 0.39).

(2) Number of Developing Defects-II In (1) Number of Developing Defects-I, the number of development defects was measured in the same manner as for the sample heated, developed, rinsed and dried except that no exposure was performed.

Examples 1 to 9 and Comparative Examples 1 to 6 [Formulation of positive photoresist composition]

Example 1 Resin: resin (B-1) obtained in Synthesis Example 5 94.92 parts by weight Photoacid generator: (A-1) 2.00 carboxylic acid derivative (C-1) of the present invention 3.00 nitrogen-containing basic compound (D-1) 0.04 surfactant (W-1) 0.04 solvent: the following (S-1) 733.33

Example 2 Resin: 91.76 parts by weight of resin (B-1) obtained in Synthesis Example 5 Photoacid generator: (A-1) 1.00 below (A-3) 2.00 The present invention Carboxylic acid derivative (C-4) 5.00 Nitrogen-containing basic compound (D-2) 0.10 Surfactant (W-4) 0.02 Solvent: the following (S-1) 513.33 The following (S -4) 220.00

Example 3 Resin: 93.88 parts by weight of resin (B-1) obtained in Synthesis Example 5 Photoacid generator: (A-2) 1.50 below (A-3) 1.50 The present invention Carboxylic acid derivative (C-6) 3.00 Nitrogen-containing basic compound (D-1) 0.10 Surfactant (W-3) 0.02 Solvent: the following (S-1) 733.33

Example 4 Resin: 93.33 parts by weight of resin (B-1) obtained in Synthesis Example 5 Photoacid generator: (A-2) 1.50 below (A-3) 4.50 The present invention Carboxylic acid derivative (C-7) 0.50 Nitrogen-containing basic compound (D-2) 0.15 Surfactant (W-2) 0.02 Solvent: (S-1) 586.66 below (S -2) 146.67

Example 5 Resin: 93.83 parts by weight of resin (B-2) obtained in Synthesis Example 6 Photoacid generator: (A-1) 3.00 Carboxylic acid derivative (C-8) of the present invention 3.00 nitrogen-containing basic compound (D-1) 0.15 surfactant (W-2) 0.02 solvent: the following (S-1) 733.33

Example 6 Resin: 94.29 parts by weight of resin (B-3) obtained in Synthesis Example 7 Photoacid generator: (A-1) 1.50 below (A-3) 3.50 The present invention Carboxylic acid derivative (C-6) 0.35 Nitrogen-containing basic compound (D-3) 0.30 Surfactant (W-1) 0.06 Solvent: (S-1) 733.33

Example 7 Resin: 90.86 parts by weight of resin (B-4) obtained in Synthesis Example 8 Photoacid generator: (A-1) 2.50 below (A-2) 0.50 The present invention Carboxylic acid derivative (C-7) 6.00 Nitrogen-containing basic compound (D-1) 0.10 Surfactant (W-2) 0.04 Solvent: (S-1) 513.33 below (S-1) -3) 220.00

Example 8 Resin: Resin (B-5) obtained in Synthesis Example 9 89.84 parts by weight Photoacid generator: (A-3) 7.00 Carboxylic acid derivative (C-6) of the present invention 3.00 nitrogen-containing basic compound (D-1) 0.15 surfactant (W-4) 0.01 solvent: the following (S-1) 733.33

Example 9 Resin: 90.72 parts by weight of resin (B-6) obtained in Synthesis Example 10 Photoacid generator: (A-1) 4.00 Carboxylic acid derivative (C-6) of the present invention 5.00 Nitrogen-containing basic compound (D-2) 0.20 Surfactant (W-3) 0.08 Solvent: (S-1) 366.67 below (S-4) 366.66

Comparative Example 1 The following composition was prepared in the same manner as in Example 1 except that itaconic anhydride described in Example 2 of JP-A-7-92679 was added and no nitrogen-containing basic compound was added. The composition was mixed to a solids concentration of about 12%. afterwards,
The solution was filtered through a 0.1 μm Teflon (registered trademark) microfilter to prepare a positive photoresist solution, a resist pattern was formed, and development defects were evaluated. Resin: 92.22 parts by weight of resin (B-1) obtained in Synthesis Example 5 Photoacid generator: (A-1) below 5.0 Itaconic anhydride 2.00 Nitrogen-containing basic compound --- Interface Activator (W-4) 0.01 Solvent: (S-1) 733.33

Comparative Example 2 The following composition was prepared in the same manner as in Example 1 except that succinic anhydride described in Example 4 of JP-A-7-92679 was added and no nitrogen-containing basic compound was added. The composition was mixed to a solids concentration of about 12%. afterwards,
The solution was filtered through a 0.1 μm Teflon microfilter to prepare a positive photoresist solution, a resist pattern was formed, and development defects were evaluated. Resin: Resin (B-1) obtained in Synthesis Example 5 91.99 parts by weight Photoacid generator: (A-1) 5.00 succinic anhydride 3.00 nitrogen-containing basic compound --- Interface Activator (W-4) 0.01 Solvent: (S-1) 733.33

Comparative Example 3 [0177] Salicylic acid and triethylamine as a nitrogen-containing basic compound described in Example 1 of JP-A-9-6001 were added, and a surfactant was not added.
A composition having the following composition was mixed so as to have a solid content of about 12%. Thereafter, the solution was filtered through a 0.1 μm Teflon microfilter to prepare a positive photoresist solution, a resist pattern was formed, and development defects were evaluated. Resin: 89.90 parts by weight of resin (B-1) obtained in Synthesis Example 5 Photoacid generator: (A-3) 7.00 salicylic acid 3.00 triethylamine 0.10 Surfactant --- Solvent: The following (S-1) 733.33

Comparative Example 4 Itaconic anhydride described in Example 2 of JP-A-7-92679 was added, dimethylamine was added as a nitrogen-containing basic compound, and a nonionic surfactant (fluorine and fluorine) was added. And / or a surfactant containing no silicon atom), and a composition having the following composition was mixed so as to have a solid concentration of about 12% in the same manner as in the Examples. afterwards,
The solution was filtered through a 0.1 μm Teflon microfilter to prepare a positive photoresist solution, a resist pattern was formed, and development defects were evaluated. Resin: Resin (B-1) obtained in Synthesis Example 5 91.99 parts by weight Photoacid generator: (A-1) 5.00 itaconic anhydride 3.00 dimethylamine 0.10 Surfactant: poly Oxyethylene nonyl phenyl ether 0.01 Solvent: the following (S-1) 733.33

Comparative Example 5 In the same manner as in Example 5 except that lauric acid and trioctylamine were added as the nitrogen-containing basic compound described in Example 5 of JP-A-10-20501, and no surfactant was added. A composition having the following composition having a solid content of about 12:
%. Thereafter, the solution was filtered through a 0.1 μm Teflon microfilter to prepare a positive photoresist solution, a resist pattern was formed, and development defects were evaluated. Resin: 92.60 parts by weight of resin (B-1) obtained in Synthesis Example 5 Photoacid generator: (A-3) 5.00 lauric acid 2.00 trioctylamine 0.40 Solvent: (S- 1) 733.33

Comparative Example 6 Perfluorooctanoic acid and trioctylamine as a nitrogen-containing basic compound described in Example 6 of JP-A-10-20501 were added, and the same as in Example except that no surfactant was added. Then, a composition having the following composition was mixed so that the solid content concentration was about 12%. Then 0.1
Filtered with a μm Teflon microfilter to prepare a positive photoresist solution, form a resist pattern,
The development defect was evaluated. Resin: 98.10 parts by weight of resin (B-1) obtained in Synthesis Example 5 Photoacid generator: (A-2) 1.50 perfluorooctanoic acid 0.30 Trioctylamine 0.10 Solvent: S-4) 733.33

The photoacid generators (A-1) to (A-3) used in Examples 1 to 9 and Comparative Examples 1 to 6, the nitrogen-containing basic compounds (D-1) to (D-3), Surfactant (W-1)-
(W-4) and the solvents (S-1) to (S-4) are as follows. The carboxylic acid derivative is as exemplified above.

[0182]

Embedded image

D-1: 1,5-diazabicyclo [4.
3.0] -5-Nonene D-2: 1,8-diazabicyclo [5.4.0] -7-
Undecene D-3: 2,4,5-triphenylimidazole

W-1: Megafac F176 (fluorine-based surfactant manufactured by Dainippon Ink and Chemicals, Inc.) W-2: Megafac R08 (fluorine / silicon-based surfactant manufactured by Dainippon Ink and Chemicals, Inc.) W-3: Polysiloxane polymer KP341 (a silicon-based surfactant manufactured by Shin-Etsu Chemical Co., Ltd.) W-4: Florado FC430 (Sumitomo 3M Limited)
Fluorinated surfactant)

S-1: propylene glycol monomethyl ether acetate S-2: propylene glycol monomethyl ether S-3: ethoxyethyl propionate S-4: ethyl lactate

[0186]

[Table 1]

As shown in Table 1, the resist composition of the present invention has few development defects. In particular, Examples 1 to
As shown in 9, when an aliphatic cyclic amine is used as the nitrogen-containing basic compound, development defects are reduced.

[0188]

According to the present invention, by blending a carboxylic acid derivative having a partial structure represented by the aforementioned general formula (I) and having a molecular weight of 1,000 or less, far ultraviolet light, particularly Kr
A positive photoresist composition which is suitable for F excimer laser light, does not cause a problem of development defects, and has excellent stability in a semiconductor manufacturing process can be provided.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03F 7/004 501 G03F 7/004 501 504 504 H01L 21/027 H01L 21/30 502R F-term (Reference) 2H025 AA04 AB16 AC04 AC08 AD03 BE00 BE07 BE10 BF15 BG00 CB45 CC04 CC20 FA17 4J002 BC121 EF017 ER028 EU048 EU078 EU088 EU098 EU128 EU138 EU148 EU186 EU216 EU238 EV216 EV256 EV296 FD206 FD207 FD208 GP03

Claims (6)

[Claims] (A) a compound which generates an acid upon irradiation with actinic rays or radiation, (B) a resin which is insoluble or hardly soluble in alkali and becomes alkali-soluble by the action of an acid,
And (C) a positive photoresist composition comprising a carboxylic acid derivative having a partial structure represented by the following general formula (I) and having a molecular weight of 1,000 or less. Embedded image In (the general formula (I), R ₁ is a hydrogen atom, a fluorine atom or -CF _3,, R ₂ is a hydrogen atom, a fluorine atom, .R ₃ representing a -CF ₃ or -O-R _3, is Carbon number 1
Represents an alkyl group of 4 to 4 or a fluoroalkyl group.
m and n each independently represent an integer of 1 to 3. A plurality of R ₁ and a plurality of R ₂ may be the same or different. However, at least one of R ₁ and R ₂ represents a fluorine atom or a group containing a fluorine atom. ) 2. The positive photoresist composition according to claim 1, wherein the carboxylic acid derivative (C) is a compound represented by the following general formula (II). Embedded image (In the above general formula (II), X represents a hydrogen atom, a fluorine atom, an alkyl group, a fluoroalkyl group, an alkoxy group, or a fluoroalkoxy group. R ₁ represents a hydrogen atom, a fluorine atom, or —CF ₃ ; R ₂ represents a hydrogen atom, a fluorine atom, —CF ₃ , or —O—R _3.
3 represents an alkyl group having 1 to 4 carbon atoms or a fluoroalkyl group. m and n each independently represent an integer of 1 to 3. A plurality of R ₁ and a plurality of R ₂ may be the same or different. However, at least one of R ₁ and R ₂ represents a fluorine atom or a group containing a fluorine atom. ) 3. The positive photoresist composition according to claim 1, wherein the resin as the component (B) contains a repeating unit represented by the following general formulas (IV) and (V). object. Embedded image (In the above formula, L is a hydrogen atom, which may be substituted;
Represents a linear, branched or cyclic alkyl group or an aralkyl group which may be substituted. Z represents a linear, branched or cyclic alkyl group which may be substituted, or an aralkyl group which may be substituted. Further, Z and L may combine to form a 5- or 6-membered ring. ) 4. The positive photoresist composition according to claim 1, further comprising (D) a nitrogen-containing basic compound. 5. The nitrogen-containing basic compound contains at least one kind of an aliphatic cyclic amine.
4. The positive photoresist composition according to item 1. 6. The composition according to claim 1, further comprising (E) a fluorine-based and / or silicon-based surfactant.
6. The positive photoresist composition according to any one of the above items 5.