JPH10260533A - Positive photoresist composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a chemically sensitized positive photoresist composition superior in storage stability and constituent solubility and coating uniformity free from occurrence of coating trouble, such as coating residues and striations by incorporating a compound to be decomposed by acid and increased in solubility in an alkaline developing solution and an acid photogenerator and an alkoxy butyl acetate. SOLUTION: This positive photoresist composition comprises the compound having a group to be decomposed by action of an acid and raised in solubility in the alkaline developing solution and the compound to be allowed to release an acid by irradiation with activated rays or radiation, and the alkoxy-butyl and/or-pentyl acetate, embodied by 3-methoxybutyl acetate, and the group to be decomposed by action of the acid and to be raised in solubility in the alkaline developing solution is embodied by one of tertiary alkyl esters and acetals and silyl ethers.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a chemically amplified positive photoresist composition, and more particularly, to a process for producing semiconductors such as ICs, a circuit substrate for liquid crystals, thermal heads, and the like. A chemically amplified positive photoresist composition for microfabrication that is suitable for use in the photofabrication process, has excellent coating performance, storage safety, and component solubility, as well as high resolution and heat resistance. It is about.

[0002]

2. Description of the Related Art Positive photoresist compositions include:
In general, a resist composition obtained by dissolving an alkali-soluble resin and a naphthoquinonediazide compound as a photosensitive material in a solvent, a compound that generates an acid upon irradiation with radiation (photoacid generator), and a compound having an acid-decomposable group A chemically amplified positive photoresist composition dissolved in a solvent is used. The chemically amplified positive photoresist composition is practically used as an effective system for shortening the wavelength of a light source because high sensitivity can be achieved despite its low absorption in the Deep-UV region. In recent years, where the degree of integration is required, it has been particularly frequently used. Conventionally, coating solvents for positive photoresists include glycol ether and glycol ether esters such as 2-methoxyethanol and 2-ethoxyethanol, and their acetates, for example, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate. And so on have been very commonly used.

[0003] However, since the solvent containing these glycol ether derivatives has been pointed out in 1979 to cause adverse effects on the reproductive function of mice, animal experiments have been repeated mainly in Europe and the United States and biotoxicity such as reproductive dysfunction has been observed. Was actually identified and reported as a potential biological threat to worker safety. (NIOH Current Intelligenc
e Bulletin, Vol.39, No.5, 1983) US Environmental Protection Agency (E
PA) recommended tightening of regulations in 1984, and the movement to tighten regulations became widespread.

[0004] In response to this fact, many photoresist manufacturers have demanded the development of photoresist products with low toxicity solvents that do not contain ethylene glycol ethers. As alternative low toxicity solvents, monooxycarboxylic acid esters such as ethyl lactate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate, and ethyl 3-ethoxypropionate (Japanese Patent Publication No. 3-22619, U.S. Pat.
S5238774, EP211667), propylene glycol monomethyl ether acetate (JP-B 3-1)
No. 659, US Pat. Besides this,
Cyclopentanone N-hexanol and diethylene glycol dimethyl ether (SEMICONDUCTORINTERNATIONA
L, Vol.4, pp132-133, 1988) and 2-heptanone (NI
KKEI MATERIALS & TECHNOLOGY Vol.12, p83-89, 199
3), ethyl pyruvate (JP-A-63-220139;
Solvents such as JP-A-4-36952, US Pat. No. 5,100,758) have been proposed. However, toxicity tests (such as tests on chronic toxicity, reproductive toxicity, teratogenicity, mutagenicity, carcinogenicity, and fate of living organisms) require a long period of time, so all of these are not necessarily proven to be safe. Not.

[0005] Originally, ethylene glycol monoethyl ether acetate is toxic because it is decomposed into 2-ethoxyethanol by biological metabolism to become ethoxyacetic acid, which is considered to be a cause of toxicity (teratogenicity). But,
For example, ethyl lactate is considered to be safe because it is decomposed into lactic acid and ethanol by biological metabolism, and is also recognized as a food additive. Ethyl-3-ethoxypropionate is converted to 3-ethoxypropionic acid, ethylmalonic acid, and malonic acid by biological metabolism and, like ethyl lactate, does not generate alkoxyacetic acid, and is therefore considered to be highly stable. . Similarly, propylene glycol monomethyl ether acetate is also converted to propylene glycol, does not produce alkoxyacetic acid, and has been confirmed to be much less toxic than the corresponding ethylene glycols.

As described above, low toxicity is one of the requirements to be satisfied by the photoresist solvent. The next important requirement to be met is coatability. 2. Description of the Related Art In recent years, the size of wafers has been increasing with the integration of LSIs and the like. As the size becomes larger, there is a problem that the uniformity of spin coating in the substrate surface is deteriorated and uncoated portion is generated, and the industrial value is reduced.

In order to improve the coating property, Japanese Patent Application Laid-Open No.
-105143, 58-203434, 62-
No. 36657 discloses a known solvent for a resist composition such as ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, N, N-dimethylformamide, dioxane, cyclohexanone, and cyclohexane. It is described that a fluorinated surfactant is blended with pentanone, γ-butyl lactone, ethyl lactate, and methyl lactate, and US Pat. No. 4,526,856 and JP-A-59-23153.
No. 4 describes combining cyclopentanone and cyclohexane with an aliphatic alcohol having 5 to 12 carbon atoms.

[0008] However, even if striation can be prevented by the above method or the like, uniformity of coating in the radial direction of the substrate (uneven thickness of the film) often poses a problem. For example, it has been pointed out that, when a resist of an ethyl lactate solvent is applied, the dispersion of the film thickness is larger than that of an ethylene glycol monoethyl ether acetate solvent (NIKKEI MATERIALS & TECHNOLOGY Vol.12, p87,
1993).

It has been reported that such coating properties are related to properties such as the evaporation rate of the solvent and the latent heat viscosity of evaporation (Semiconductor World, Vol. 1, p125-128, 199).
1) To solve this problem, mixing ethyl lactate and ethyl 3-ethoxypropionate,
504422, US-5063138 EP44295
2, WO 90/05325), a mixture of ethyl lactate and isoamyl acetate or n-amyl acetate (US Pat. No. 5,336,583,
EP 510670, JP-A-5-34918), a mixture of ethyl lactate with anisole and amyl acetate (US Pat. No. 5,128,282)
30) and so on have been devised so far.

This coating property can be improved to some extent by improving the coating apparatus, that is, by optimizing the conditions such as the coating atmosphere temperature, the substrate temperature, the coating resist temperature, and the exhaust gas. Regardless, it is most preferable to obtain uniform coating properties. Apart from the above-mentioned problems, if the photoresist composition is left after being filtered, for example, with a filter having a pore size of 0.2 μm, fine particles that cannot be visually observed precipitate, and the resist composition with the fine particles deposited is stored for a longer period of time. Then, eventually, precipitation may occur.

When a resist pattern is formed on a wafer using a resist composition containing such fine particles, fine particles remain in portions where the resist is to be removed by development, and there is a problem that the resolution is reduced. In order to improve the stability over time, Japanese Patent Application Laid-Open No. 61-260239
No. 1-293340, N-methyl-2-
Pyrrolidone, dimethyl sulfoxide, dimethyl formamide, dimethyl malonate, ethyl cyanoacetate,
High boiling point (180-220 ° C) like butanediol
It discloses that a solvent having a solubility parameter of 11 to 12 is mixed.

Further, Japanese Patent Application Laid-Open Nos. Sho 62-123444 and 6
In 3-220139, for example, methyl 2-methoxyacetate, methyl 2-ethoxyacetate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate,
Ethyl ethoxypropionate, methyl 3-methoxypropionate, propyl 2-hydroxypropionate, 2-
Storage stability of resist solution by using a solvent containing monooxymonocarboxylic acid esters such as ethyl methoxypropionate, propyl 2-ethoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, etc. JP-A-59-155838 discloses that cyclopentanone is particularly effective in improving (prevention of precipitation over time).

As described above, no precipitate is generated over time,
Good storage stability is a third requirement for photoresist solvents.

Further, when the photoacid generator or the acid-decomposable group is decomposed during storage, there is a risk that the sensitivity may be changed or the photoresist container (glass bottle) may be broken by the internal pressure. Therefore, a photoacid generator or a solvent that does not decompose the acid-decomposable group is preferable. Other requirements that must be met include low hygroscopicity of the solvent and monthly Semiconductor World Vol.1, p125-12
8, 1991, resist properties (sensitivity, resolution, profile, scum, adhesion, heat resistance)
Is preferable. For example, JP-A-5-17
As described in No. 3329, ethyl lactate and the like easily absorb moisture during a photoresist preparation step and a coating step. The photoresist that has absorbed moisture deteriorates various properties of the resist.

Further, in a chemically amplified resist composition, a compound having an acid-decomposable group such as an acetal group has a problem in storage stability that the compound is decomposed when the composition is stored over time. Was. Furthermore, in a chemically amplified resist composition, a low molecular weight dissolution inhibiting compound having an acid-decomposable group (non-polymer type dissolution inhibiting compound) was not sufficiently soluble in a conventional solvent.

As described above, in the chemically amplified resist composition, the coating performance, the solubility of the components, the storage stability of the solution, and the resist performance are attributed to the components such as the photoacid generator and the binder polymer. At the same time, it is known that the properties are greatly influenced by the solvent. However, there are few known solvents that simultaneously satisfy all of the coating performance, component solubility, solution storage stability, safety, and resist performance.

[0017]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a chemically amplified positive photoresist composition which is excellent in storage stability and component solubility, free from residual coating and has no troubles such as striation, and excellent in coating uniformity. To provide things.

Further, another object of the present invention is to provide excellent solubility in each component, excellent storage stability of the solution, no precipitation or decomposition of fine particles of each component during storage, and
An object of the present invention is to provide a chemically amplified positive photoresist composition having excellent heat resistance.

[0019]

Means for Solving the Problems The inventors of the present invention have paid careful attention to the above-mentioned various properties, and as a result of intensive studies, have found that a photoresist composition using a specific compound as a solvent has a specific coating performance,
They have found that they are excellent in solubility, storage stability, and resist performance, and have completed the present invention.

That is, the object of the present invention is achieved by the following constitution. (1) (a) a compound having a group which is decomposed by the action of an acid to increase solubility in an alkali developer, (b) a compound which generates an acid upon irradiation with actinic rays or radiation, and (c) an alkoxy. A positive photoresist composition comprising butyl acetate and / or alkoxypentyl acetate. (2) The positive photoresist composition as described in (1) above, wherein the alkoxybutyl acetate is 3-methoxybutyl acetate. (3) The positive photoresist composition as described in the above (1), wherein (c) is an alkoxyalkylbutyl acetate and / or an alkoxyalkylpentyl acetate. (4) The positive photoresist composition according to (3), wherein the alkoxyalkylbutyl acetate contains 3-methoxy-3-methylbutyl acetate.

(5) The above (a) is decomposed by the action of an acid and decomposed by a polymer type compound having a group that increases the solubility in an alkali developer and / or an action of an acid. The positive photoresist composition according to the above (1), which is a non-polymer type compound having a group that increases the solubility in the composition. (6) at least one group selected from a tertiary alkyl ester group and a tertiary alkyl carbonate group, wherein the group which decomposes under the action of the acid of (a) and increases the solubility in an alkaline developer; And / or at least one selected from an acetal group and a silyl ether group.

[0022]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
Examples of the alkoxybutyl acetate and / or alkoxypentyl acetate of the present invention include 3-methoxybutyl acetate, 3-ethoxybutyl acetate, 4-methoxypentyl acetate, and 4-ethoxypentyl acetate. Further, these may have a substituent such as an alkyl group or an alkoxy group. Examples of the alkoxybutyl acetate and / or alkoxypentyl acetate having a substituent include alkoxyalkyl butyl acetate and / or alkoxyalkyl pentyl acetate, dialkoxybutyl acetate and / or dialkoxypentyl acetate.
-Methoxy-3-methylbutyl acetate, 3-ethoxy-3-methylbutyl acetate, 4-methoxy-4-
Examples include methylpentyl acetate, 4-ethoxy-4-methylpentyl acetate, 3,3′-dimethoxy-butyl acetate, and 4,4′-dimethoxy-pentyl acetate. As the above-mentioned alkoxybutyl acetate, 3-methoxybutyl acetate, 3-ethoxybutyl acetate, and 3-methoxy-3-methylbutyl acetate are preferred, and 3-methoxy-3-methylbutyl acetate is particularly preferred.

The alkoxybutyl acetate and alkoxypentyl acetate of the present invention are used in an amount of 3 to 1900 parts by weight, preferably 10 to 1900 parts by weight, more preferably 20 to 120 parts by weight, based on 100 parts by weight of the solid content in the resist solution.
Used in a proportion of 0 parts by weight. In the present invention, it is preferable to mainly use the alkoxybutyl acetate and / or alkoxypentyl acetate solvent. However, 2 to 100% of the total amount of the solvent in the positive resist composition
The other solvent can be mixed in a range of less than 98% by weight, preferably less than 50% by weight, more preferably less than 30% by weight of the total amount of the solvent.

Specific examples of other solvents that can be mixed include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol isopropyl ether,
Ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol mono-n-butyl ether,
Ethers such as dipropylene glycol monomethyl ether, benzyl ethyl ether and dihexyl ether;
Methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, ethyl acetate, butyl acetate, amyl acetate,
Esters such as hexyl acetate, butyl propionate, amyl propionate, propyl butyrate, butyl butyrate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate, propylene carbonate, γ-butyrolactone, γ-valerolactone, methyl ethyl ketone, diethyl -Iso-butyl ketone, methyl-iso-butyl ketone, methyl-n
-Butyl ketone, di-iso-propyl ketone, methyl-n-amyl ketone, methyl-iso-amyl ketone,
3-methyl-2-hexanone, 4-methyl-2-hexanone, methyl-n-hexylketone, methyl-iso-
Aliphatic ketones such as hexyl ketone, 4-methyl-2-heptanone, 5-methyl-2-heptanone, 3-heptanone, 4-heptanone, 2,6-dimethyl-4-heptanone, cyclobutanone, cyclopentanone, and cyclohexanone Etc., diketones such as acetylacetone and acetonylacetone, 1-methoxy-2-butanone, 1-ethoxy-2-butanone, 1-methoxy-3
-Pentanone, 1-ethoxy-3-pentanone, 1-methoxy-2-pentanone, 1-ethoxy-2-pentanone, 4-n-propoxy-2-propanone, 4-iso
-Propoxy-2-propanone, 4-methoxy-2-butanone, 4-ethoxy-2-butanone, 4-n-propoxy-2-butanone, 4-iso-propoxy-2-butanone, 5-methoxy-2-pentanone , 5-ethoxy-2-pentanone, 5-methoxy-4-methyl-2-pentanone, 5-methoxy-3-methyl-2-pentanone, 5-methoxy-4-methyl-2-pentanone, 4-
Methoxy-4-methyl-2-pentanone, 4-ethoxy-4-methyl-2-pentanone, 4-ethoxy-4-methyl-2-butanone, 4-ethoxy-3-methyl-2-
Ketoales such as butanone, 4-hydroxy-2-butanone, 3-hydroxy-2-butanone, 3-hydroxy-2-pentanone, 5-hydroxy-2-pentanone,
3-hydroxy-2-hexanone, 4-hydroxy-3
-Ketols such as -methyl-2-butanone, 3-hydroxy-3-methyl-2-butanone, 4-hydroxy-4-methyl-2-pentanone, butyl alcohol, n-amyl alcohol, iso-amyl alcohol, benzyl alcohol , Cyclohexanol, alcohols such as furfuryl alcohol, methyl 2-methoxyacetate, ethyl 2-ethoxyacetate, methyl 2-hydroxypropionate,
Ethyl 2-hydroxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, 3
-Ethyl methoxypropionate, methyl 3-ethoxypropionate, propyl 2-hydroxypropionate, 2
-Ethyl methoxypropionate, propyl 2-ethoxypropionate, methyl 2-ethoxypropionate, 2-
Monooxycarboxylic acid esters such as ethyl ethoxypropionate, methyl β-methoxyisobutyrate, and methyl α-hydroxyisobutyrate; aromatic hydrocarbons such as toluene, xylene, ethylbenzene, and anisole; methyl pyruvate; and ethyl pyruvate. Highly polar solvents such as diketone solvents, dimethylacetamide, N-methylpyrrolidone, dimethylformamide, dimethylsulfoxide and the like can be mentioned.

Among them, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 2-hydroxypropionate, methyl β-methoxyisobutyrate, propylene glycol Methyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, propylene glycol monomethyl ether, isoamyl propionate, isoamyl acetate,
N-butyl acetate, 2-heptanone, 2-methoxy-2-
Methyl-4-pentanone and the like are particularly preferred.

In the present invention, it is decomposed by the action of an acid,
Compounds having a group that increases the solubility in an aqueous alkali solution (dissolution inhibiting compounds) include alkali-soluble resins (polymer type dissolution inhibiting compounds) and / or non-polymer type dissolution inhibiting compounds containing these acid-decomposable groups. Including.

Here, the non-polymer type dissolution inhibiting compound is a compound having a constant molecular weight of 3000 or less and having a structure in which an acid-decomposable group is introduced into a compound having a single structure. A compound that becomes alkali-soluble. Further, the polymer-type dissolution inhibiting compound is a compound obtained by polymerizing a monomer, having a structure in which an acid-decomposable group is introduced into a compound having a molecular weight distribution and being alkali-soluble by the action of an acid. . In the present invention, an alkali-soluble resin containing no acid-decomposable group can be used in combination with the above-mentioned compound containing an acid-decomposable group. In the positive photoresist composition of the present invention, when the compound containing an acid-decomposable group is a non-polymer type dissolution inhibiting compound alone, it is preferable to use an alkali-soluble resin containing no acid-decomposable group in combination. When an alkali-soluble resin not containing an acid-decomposable group is used in combination, it is more preferable that the compound containing an acid-decomposable group contains both a polymer-type dissolution-inhibiting compound and a non-polymer-type dissolution-inhibiting compound.

In a preferred embodiment of the present invention,
A group which can be decomposed by⁰, -OB⁰
As a group containing a group, -R⁰-COO-A⁰Or -A
r-OB⁰The group shown by these is mentioned. Where A
⁰Is -C (R⁰¹) (R⁰²) (R⁰³), -Si (R⁰¹)
(R⁰²) (R ⁰³) Or -C (R⁰⁴) (R⁰⁵) -O-
R⁰⁶Represents a group. B⁰Is A⁰Or -CO-OA⁰Base
Show.

[0029] ^{R 01, R 02, R 03} , R 04 and R ⁰⁵ may also be different from, and each of the same, shows a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group, R ⁰⁶ Represents an alkyl group or an aryl group. However, at least two of R ^{01 to} R ⁰³ are groups other than a hydrogen atom, and two groups of R ^{01 to} R ⁰³ and R ^{04 to} R ⁰⁶ are bonded to form a ring. Is also good. R ⁰ represents a divalent or higher valent aliphatic or aromatic hydrocarbon group which may have a substituent, and -Ar- is a divalent or higher valent which may have a monocyclic or polycyclic substituent. Shows an aromatic group.

Here, the alkyl group preferably has 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.

Examples of the substituent include a hydroxyl group, a halogen atom (fluorine, chlorine, bromine, iodine), a nitro group, a cyano group, and the above-mentioned alkyl groups, methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group. Alkoxy groups such as groups, n-butoxy group, isobutoxy group, sec-butoxy group, t-butoxy group, alkoxycarbonyl groups such as methoxycarbonyl group and ethoxycarbonyl group, aralkyl groups such as benzyl group, phenethyl group and cumyl group, Aralkyloxy groups, formyl groups, acetyl groups, butyryl groups, benzoyl groups, cyanyl groups, acyl groups such as valeryl groups, acyloxy groups such as butyryloxy groups, the above alkenyl groups, vinyloxy groups, propenyloxy groups, allyloxy groups, butenyloxy groups Alkenyloxy groups such as Serial aryl group, an aryloxy group such as phenoxy group, and an aryloxycarbonyl group such as 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 group. Alkyl ester groups, tertiary alkyl carbonate groups and the like. More preferred are a tertiary alkyl ester group, a tertiary alkyl carbonate group, a cumyl ester group and a tetrahydropyranyl ether group.

In particular, the acid-decomposable group is at least one of (A) a silyl ether group and an acetal group, and / or
Alternatively, it is preferable that (B) be at least one of a tertiary alkyl ester group and a tertiary alkyl carbonate group. Further, as the acid-decomposable group (B), a tertiary alkyl ester group is more preferable than a tertiary alkyl carbonate group. As a result, the balance between the pattern forming ability and performance of the resist, the storage stability, and the coating uniformity becomes better.

Specific examples of the tertiary alkyl group of the tertiary alkyl ester group and the tertiary alkyl carbonate group include a t-butyl group, a t-pentyl group, a t-hexyl group,
Particularly preferred is a t-butyl group. Also, as the acetal group,

[0035]

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A group represented by the following formula, particularly preferably

[0037]

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The following groups may be mentioned. Further, as a silyl ether group,

[0039]

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The following groups can be mentioned.

Hereinafter, the compounds used in the present invention will be described in detail. In the non-polymeric dissolution inhibiting compound used in the present invention, at least two acid-decomposable groups are present in the structure of each compound. A compound having at least 10, preferably at least 11, and more preferably at least 12 bonding atoms excluding decomposable groups, or at least three acid-decomposable groups, and the distance between the acid-decomposable groups is the most. It is advantageous to use compounds which, at remote positions, pass through at least 9, preferably at least 10, and more preferably at least 11, the linking atom exclusive of the acid-decomposable group.

The non-polymer type dissolution inhibiting compound suppresses the solubility of the alkali-soluble resin in alkali, and the acid generated upon exposure to light causes the acid-decomposable group to be deprotected. Has the effect of promoting JP-A-63-27829 and JP-A-3-198059 disclose a dissolution inhibiting compound having a skeleton compound of naphthalene, biphenyl and diphenylcycloalkane, but have a small dissolution inhibiting property for an alkali-soluble resin, and have a high profile and resolution. Is not enough.

In the present invention, a preferred non-polymeric dissolution inhibiting compound is a single-structure compound having a molecular weight of 3,000 or less having three or more alkali-soluble groups in one molecule, wherein at least 80% of the alkali-soluble group is an acid-decomposable group. Is a compound protected by

In the present invention, the upper limit of the number of the bonding atoms is preferably 50, more preferably 30. In the present invention, when the non-polymer type dissolution inhibiting compound has three or more, preferably four or more acid-decomposable groups, and even if it has two acid-decomposable groups, the acid-decomposable groups are mutually present. If they are separated by a certain distance or more, the dissolution inhibiting property with respect to the alkali-soluble resin is significantly improved.

The distance between the acid-decomposable groups in the present invention is represented by the number of via-bond atoms excluding the acid-decomposable groups. For example, in the case of the following compounds (1) and (2), the distance between the acid-decomposable groups is 4 bonding atoms, and in the compound (3), the bonding atom is 12 bonding atoms.

[0046]

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The non-polymeric dissolution-inhibiting compound of the present invention may have a plurality of acid-decomposable groups on one benzene ring, but preferably has one acid-decomposable group on one benzene ring.
It is a compound composed of a skeleton having two acid-decomposable groups. Further, the molecular weight of the non-polymeric dissolution inhibiting compound of the present invention is 3,500 or less, preferably 500 to 3,0.
00, more preferably 1,000 to 2,500.
When the molecular weight of the non-polymeric dissolution inhibiting compound of the present invention is in the above range, it is preferable in terms of high resolution.

Preferred non-polymeric dissolution inhibiting compounds are
JP-A-1-289946, JP-A-1-289947
JP-A-2-2560, JP-A-3-128959
JP-A-3-158855, JP-A-3-17935
No. 3, JP-A-3-191351, JP-A-3-2002
No. 51, JP-A-3-200252, JP-A-3-200
No. 253, JP-A-3-200254, JP-A-3-20
0255, JP-A-3-259149, JP-A-3-2
No. 79958, JP-A-3-279959, JP-A-4-
1650, JP-A-4-1651, JP-A-4-112
No. 60, JP-A-4-12356, JP-A-4-1235
No. 7, Japanese Patent Application No. 3-33229, Japanese Patent Application No. 3-23079
No. 0, Japanese Patent Application No. 3-320438, Japanese Patent Application No. 4-2515
7, Japanese Patent Application No. 4-52732, Japanese Patent Application No. 4-10321
No. 5, Japanese Patent Application No. 4-104542, Japanese Patent Application No. 4-1078
No. 85, Japanese Patent Application Nos. 4-107889 and 4-15219
A part of or all of the phenolic OH groups of the polyhydroxy compound described in the specification such as No. 5 above;
-R ⁰ -COO-A ⁰ or a compound bonded and protected by a B ⁰ group is included.

More preferably, JP-A-1-289946.
JP-A-3-128959, JP-A-3-15885
5, JP-A-3-179353, JP-A-3-2002
No. 51, JP-A-3-200252, JP-A-3-200
255, JP-A-3-259149, JP-A-3-27
9958, JP-A-4-1650, JP-A-4-112
No. 60, JP-A-4-12356, JP-A-4-1235
7, Japanese Patent Application No. 4-25157, Japanese Patent Application No. 4-10321
No. 5, Japanese Patent Application No. 4-104542, Japanese Patent Application No. 4-1078
No. 85, Japanese Patent Application Nos. 4-107889 and 4-15219
No. 5 using the polyhydroxy compound described in the specification.

More specifically, general formulas [I] to [XV]
The compound represented by I] is mentioned.

[0051]

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[0052]

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[0053]

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[0054]

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R ¹⁰¹ , R ¹⁰² , R ¹⁰⁸ , R ¹³⁰ may be the same or different, and represent a hydrogen atom, —R ⁰ —COO—C
( ^R01 ) ( ^R02 ) ( ^R03 ) or -CO-OC ( ^R01 )
^{(R 0 2) (R 03} ), provided that the definition of R ^0, R ^01, R ⁰² and R ⁰³ are as defined above.

R ¹⁰⁰ : -CO-, -COO-, -NHC
ONH-, -NHCOO-, -O-, -S-, -SO
-, -SO _2- , -SO _3- , or

[0057]

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[0058] Here, G = 2 to 6, provided that at least one alkyl group of R ^0.99, R ¹⁵¹ when the ^{G = 2, R 150, R} 151: may be the same or different, a hydrogen atom, an alkyl Group, alkoxy group, -OH, -COOH,
-CN, halogen atom, -R ¹⁵² -COOR ^{15 3} or ^{-R 154 -OH, R 152, R} 154: an alkylene group, R ^153: a hydrogen atom, an alkyl group, an aryl group or an aralkyl group,, R ^99, R ¹⁰³ To R ¹⁰⁷ , R ¹⁰⁹ , R ^{111 to} R ¹¹⁸ , R
^{121 to} R ¹²³ , R ^{128 to} R ¹²⁹ , R ^{131 to} R ¹³⁴ , R
^{138 to} R ¹⁴¹ and R ¹⁴³ may be the same or different and include a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, an acyl group, an acyloxy group, an aryl group, an aryloxy group, an aralkyl group, an aralkyloxy group, a halogen atom, nitro Group, carboxyl group, cyano group, or -N ( ^R155 )
(R ¹⁵⁶ ) (R ¹⁵⁵ , R ¹⁵⁶ : H, alkyl group or aryl group) R ¹¹⁰ : single bond, alkylene group, or

[0059]

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R ¹⁵⁷ and R ¹⁵⁹ may be the same or different, and represent a single bond, an alkylene group, —O—, —S—, —CO
— Or a carboxyl group, R ¹⁵⁸ : a hydrogen atom, an alkyl group, an alkoxy group, an acyl group, an acyloxy group, an aryl group, a nitro group, a hydroxyl group, a cyano group, or a carboxyl group, provided that the hydroxyl group is an acid-decomposable group (for example, t-butoxycarbonylmethyl group, tetrahydropyranyl group, 1-ethoxy-1-ethyl group,
(1-t-butoxy-1-ethyl group).

R ¹¹⁹ and R ^120, which may be the same or different, are a methylene group, a lower alkyl-substituted methylene group, a halomethylene group, or a haloalkyl group, provided that the lower alkyl group means an alkyl group having 1 to 4 carbon atoms. R ^{124 to} R ¹²⁷ may be the same or different and may be a hydrogen atom or an alkyl group; R ^{135 to} R ¹³⁷ may be the same or different and a hydrogen atom;
An alkyl group, an alkoxy group, an acyl group, or an acyloxy group, R ¹⁴² : a hydrogen atom, —R ⁰ —COO—C (R ⁰¹ )
( ^R02 ) ( ^R03 ) or -CO-OC ( ^R01 ) ( ^R02 )
(R ⁰³ ), or

[0062]

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R ¹⁴⁴ and R ¹⁴⁵ may be the same or different and represent a hydrogen atom, a lower alkyl group, a lower haloalkyl group,
Or an aryl group, R ^{146 to} R ¹⁴⁹ : may be the same or different and represent a hydrogen atom, a hydroxyl group, a halogen atom, a nitro group, a cyano group, a carbonyl group, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an aralkyl group, and an aralkyloxy group. A group, an acyl group, an acyloxy group, an alkenyl group, an alkenyloxy group, an aryl group, an aryloxy group, or an aryloxycarbonyl group, provided that the four substituents having the same symbol need not be the same group. : —CO— or —SO ₂ —, Z, B: single bond or —O—, A: methylene group, lower alkyl-substituted methylene group, halomethylene group, or haloalkyl group; E: single bond or oxymethylene group , A to z, a1 to y1: at plural times, the groups in () may be the same or different; a to q, s, t, v, g1 to i1, k1 m1, o1, q1, s1, u1: 0 or an integer of 1 to 5, r, u, w, x, y, z, a1~f1, p1, r1, t1, v1~x1: 0 or 1
An integer of 4, j1, n1, z1, a2, b2, c2, d2: an integer of 0 or 1 to 3, z1, a
2, at least one of c2, d2 is 1 or more, y1: an integer of 3 to 8, (a + b), (e + f + g), (k + l + m), (q + r + s ), (w
+ x + y), (c1 + d1), (g1 + h1 + i1 + j1), (o1 + p1), (s1 + t1) ≧ 2,
(j1 + n1) ≦ 3, (r + u), (w + z), (x + a1), (y + b1), (c1 + e1), (d1
+ f1), (p1 + r1), (t1 + v1), (x1 + w1) ≦ 4, provided that the general formula [V]
In the case of (w + z), (x + a1) ≦ 5, (a + c), (b + d), (e + h), (f + i),
(g + j), (k + n), (l + o), (m + p), (q + t), (s + v), (g1 + k1), (h1 + l
1), (i1 + m1), (o1 + q1), (s1 + u1) ≦ 5.

[0064]

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[0065]

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[0066]

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[0067]

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Specific examples of preferred compound skeletons are shown below.

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[0069]

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[0070]

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[0071]

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[0072]

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[0073]

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[0074]

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[0075]

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[0076]

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[0077]

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[0078]

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[0079]

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[0080]

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[0081]

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[0082]

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[0083]

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[0084]

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[0085]

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[0086]

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R in the compounds (1) to (63) is a hydrogen atom,

[0088]

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Represents the following. However, at least two or three depending on the structure are groups other than hydrogen atoms, and each substituent R in the same molecule may not be the same group. The use of the non-polymeric dissolution inhibiting compound as a mixture of two or more non-polymeric dissolution inhibiting compounds having different core nuclei structures can reduce line width slimming (expansion) and T-time between exposure and PEB. This is effective in reducing top formation. However, this effect is not related to the type of the solvent used for the resist solution. Preferred combinations in the two cases are described below, but the present invention is not limited to the two combinations. Such preferred combinations include 1
The number of acid-decomposable groups in the molecule is four or more and three or less, or three and two. As a more specific compound combination, the compound represented by the general formula (XIV)
And a compound represented by formula (I) or (I
Combination with the compound represented by the formula (I) or the general formula (I)
And a combination of a compound represented by the general formula (II). When two or more non-polymeric dissolution inhibiting compounds are used in combination, the mixing ratio is 1
The ratio of the largest number of acid-decomposable groups in the molecule (based on the weight of all non-polymeric dissolution inhibiting compounds) is 50%.
It is preferred that the content be at least 10% by weight.

In the present invention, the amount of the non-polymeric dissolution inhibiting compound to be added is 3 to 50% by weight, preferably 5 to 5% by weight, based on the total weight of the photosensitive composition (excluding the solvent).
-40% by weight, more preferably 5-35% by weight.

The alkali-soluble resin containing no acid-decomposable group (hereinafter simply referred to as “alkali-soluble resin”) used in the present invention is an alkali-soluble resin (preferably,
Polyhydroxystyrene, novolak resin, derivatives thereof, and alkali-soluble resins containing p-hydroxystyrene units (preferably poly (p-hydroxystyrene, p / m-hydroxystyrene, p / o-hydroxystyrene, p-hydroxy Styrene-styrene copolymer), 4-hydroxy-3-methylstyrene resin, 4
It is preferably an alkyl-substituted hydroxy resin such as -hydroxy-3,5-dimethylstyrene resin, or an alkylated or acetylated product of the OH portion of the resin.

Further, when a part of the phenol nucleus (30 mol% or less of the whole phenol nucleus) of the above resin is hydrogenated, the transparency of the resin is improved, which is preferable in terms of sensitivity, resolution, and rectangular formation of profile. . As the alkali-soluble resin used in the present invention, for example, novolak resin,
Hydrogenated novolak resin, acetone-pyrogallol resin,
Polyhydroxystyrene, halogen- or alkyl-substituted polyhydroxystyrene, hydroxystyrene-N-
Substituted maleimide copolymer, partially O-alkylated or O-acylated polyhydroxystyrene, styrene-maleic anhydride copolymer, carboxyl group-containing methacrylic resin and derivatives thereof, styrene-polyhydroxystyrene copolymer, Examples include, but are not limited to, hydrogenated polyhydroxystyrene.

Particularly preferred alkali-soluble resins for use in the present invention are novolak resins and alkali-soluble resins containing p-hydroxystyrene units (preferably poly (p-hydroxystyrene, p / m-hydroxystyrene, p / o- Hydroxystyrene, p-hydroxystyrene-styrene copolymer), 4-hydroxy-3-
Alkyl-substituted hydroxy resins such as methylstyrene resin, 4-hydroxy-3,5-dimethylstyrene resin,
An alkylated or acetylated product of the OH portion of the above resin, a partially hydrogenated polyhydroxystyrene resin, a polyhydroxystyrene resin, a partially hydrogenated novolak resin, and a partially hydrogenated polyhydroxystyrene resin.

In the present invention, polyhydroxystyrene refers to a p-hydroxystyrene monomer, an m-hydroxystyrene monomer, an o-hydroxystyrene monomer or a hydroxystyrene monomer having an ortho-substituted alkyl group having 1 to 4 carbon atoms. It shows a polymer obtained by polymerizing at least one kind of monomer selected from the above.

The novolak resin is obtained by subjecting a predetermined monomer as a main component to addition condensation with an aldehyde in the presence of an acidic catalyst.

As the predetermined monomer, phenol, m
Cresols such as -cresol, p-cresol and o-cresol, xylenols such as 2,5-xylenol, 3,5-xylenol, 3,4-xylenol and 2,3-xylenol, m-ethylphenol, p- Alkylphenols such as ethylphenol, o-ethylphenol, pt-butylphenol, p-octylphenol, 2,3,5-trimethylphenol, p-methoxyphenol, m-methoxyphenol, 3,5-dimethoxyphenol, Alkoxyphenols such as -methoxy-4-methylphenol, m-ethoxyphenol, p-ethoxyphenol, m-propoxyphenol, p-propoxyphenol, m-butoxyphenol and p-butoxyphenol, 2-methyl-4-isopropyl Fenault Bis-alkylphenols etc., m
Hydroxychloro compounds such as -chlorophenol, p-chlorophenol, o-chlorophenol, dihydroxybiphenyl, bisphenol A, phenylphenol, resorcinol, and naphthol can be used alone or as a mixture of two or more, but are not limited thereto. It is not something to be done.

The aldehydes include, for example, formaldehyde, paraformaldehyde, acetaldehyde, propylaldehyde, benzaldehyde, phenylacetaldehyde, α-phenylpropylaldehyde, β-phenylpropylaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde , O-chlorobenzaldehyde,
m-chlorobenzaldehyde, p-chlorobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde, p-nitrobenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-
Methylbenzaldehyde, p-ethylbenzaldehyde, pn-butylbenzaldehyde, furfural,
Chloroacetaldehyde and its acetal form, such as chloroacetaldehyde diethyl acetal, can be used, and among these, formaldehyde is preferably used.

These aldehydes are used alone or in combination of two or more. As the acidic catalyst, hydrochloric acid, sulfuric acid, formic acid, acetic acid, oxalic acid and the like can be used. The content of the alkali-soluble resin not containing an acid-decomposable group used in the present invention is from 0 to 80% by weight, preferably from 10 to 70% by weight, based on the total weight of the solid content of the composition of the present invention. % By weight.

The polymer-type dissolution inhibiting compound of the present invention includes
It is a resin having an acid-decomposable group in the main chain or side chain of the base resin, or in both the main chain and the side chain. Among them, a resin having an acid-decomposable group in a side chain is more preferable. As the polymer-type dissolution inhibiting compound of the present invention, at least one selected from an acetal group and a silyl ether group on a main chain or a side chain of the base resin, or on both the main chain and the side chain.
It is preferable to use a resin having a kind of acid-decomposable group,
Among them, a resin having an acid-decomposable group in a side chain is particularly preferable.

Next, when the acid-decomposable group is bonded as a side chain, the base resin may have -OH or-
COOH, in particular, -R ⁰ -COOH or -AR-O
An alkali-soluble resin having an H group is preferable, for example,
The alkali-soluble resin containing no acid-decomposable group used in the present invention (hereinafter simply referred to as alkali-soluble resin).
(Preferably, polyhydroxystyrene, a novolak resin, a derivative thereof) and an alkali-soluble resin containing a p-hydroxystyrene unit (preferably, poly (p
-Hydroxystyrene, p / m-hydroxystyrene,
p / o-hydroxystyrene), p-hydroxystyrene-styrene copolymer), alkyl-substituted hydroxy resins such as 4-hydroxy-3-methylstyrene resin, 4-hydroxy-3,5-dimethylstyrene resin, and the above resins Is preferably an alkylated or acetylated OH moiety.

Further, when a part of the phenol nucleus (30 mol% or less of all phenol nuclei) of the above resin is hydrogenated, the transparency of the resin is improved, and it is preferable in terms of sensitivity, resolution, and rectangular formation of profile. . Examples of the alkali-soluble resin used as the base resin include, for example, novolak resin, hydrogenated novolak resin, acetone-pyrogallol resin, polyhydroxystyrene, halogen- or alkyl-substituted polyhydroxystyrene, hydroxystyrene-N-substituted maleimide copolymer, Partially O-alkylated or O-acylated hydroxystyrene, styrene-maleic anhydride copolymer, carboxyl group-containing methacrylic resin and derivatives thereof, styrene-polyhydroxystyrene copolymer, hydrogenated polyhydroxystyrene However, the present invention is not limited to these.

Particularly preferred alkali-soluble resins used as the base resin include novolak resins and alkali-soluble resins containing p-hydroxystyrene units (preferably poly (p-hydroxystyrene, p / m-
Hydroxystyrene, p / o-hydroxystyrene, p
-Hydroxystyrene-styrene copolymer), 4-hydroxy-3-methylstyrene resin, 4-hydroxy-
Alkyl-substituted hydroxy resins such as 3,5-dimethylstyrene resin, alkylated or acetylated OH portion of the resin, partially hydrogenated polyhydroxystyrene resin, polyhydroxystyrene resin, partially hydrogenated novolak resin,
Partially hydrogenated polyhydroxystyrene resin. It is a resin obtained by reacting a polyhydroxy compound, a resin having a phenolic hydroxyl group, and a vinyl compound.

Here, polyhydroxystyrene refers to p
-Hydroxystyrene monomer, m-hydroxystyrene monomer, o-hydroxystyrene monomer or at least one or more monomers selected from alkylstyrene-substituted hydroxystyrene monomers having an ortho-position of 1 to 4 carbon atoms. The polymer obtained by the above is shown. Polyhydroxystyrene is particularly preferred as the resin having a phenolic hydroxyl group.

The alkali dissolution rate of the alkali-soluble resin for the base resin was determined by measuring with 0.261N tetramethylammonium hydroxide (TMAH) (23 ° C.) to 1
Those at 70 ° / sec or more are preferred. Particularly preferably 33
0Å / sec or more (Å is Angstroms).
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, a 248 nm film having a thickness of 1 μm
Is 20 to 80%.

From these viewpoints, particularly preferred alkali-soluble resins for the base resin are polyhydroxystyrene,
Hydrogenated polyhydroxystyrene, halogen- or alkyl-substituted polyhydroxystyrene, partially o-acylated polyhydroxystyrene, hydroxystyrene-styrene copolymer and hydrogenated novolak resin, polyhydroxy compound and resin having phenolic hydroxyl group and vinyl It is a resin obtained by reacting a compound.

In the present invention, the resin having an acid-decomposable group is disclosed in European Patent No. 2,485,853, JP-A-2-25850.
No. 3,223,860, 4-251259, etc., an 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. Can be obtained by copolymerization with various monomers.

The general formulas of the resin having an acid-decomposable group thus synthesized are shown below in (a) to (f), but the present invention is not limited to these.

[0108]

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Here, L: -R⁰-COO-C (R⁰¹) (R⁰²) (R⁰³),-
O-CO-OC (R ⁰¹) (R⁰²) (R⁰³) (However, R
⁰, R⁰¹, R⁰², R⁰³Is the same as the definition above) R₁: R in the same molecule₁Are the same or different
Or a hydrogen atom or C₁~ C_FourAn alkyl group of R_Two, R_Four: Even if the groups with the same name in the same molecule are the same
May be different, a hydrogen atom or C₁~ C_FourAl
Kill group, R_Three: Hydrogen atom, carboxyl group, cyano group or position
Substituted aryl group, R_Five: Hydrogen atom, cyano group or -COOR₆, R₆: C₁~ C_TenA linear, branched or cyclic alkyl group of₇~ R₉: Hydrogen atom or C₁~ C_FourAr: a monocyclic or polycyclic substituent which may have 1
Valent aromatic group, k, l, k1, l1, m: each independently represents a natural number, n: 0 or 1.

More specifically, the following (i) to (xxi)
i) can be mentioned.

[0111]

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[0112]

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[0113]

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The content of the acid-decomposable group is represented by B / (B + S), where the number (B) of the acid-decomposable groups in the resin and the number (S) of the alkali-soluble groups not protected by the acid-decomposable groups. expressed. The content is 0.10 to 0.40, preferably 0.15
To 0.35, more preferably 0.20 to 0.35. When B / (B + S)> 0.4, the film shrinks after PEB, and the profile at the time of defocusing becomes an inverse taper.
Defocus latitude with isolated line becomes narrower,
It is not preferable because it causes poor adhesion to the substrate and scum. On the other hand, if B / (B + S) <0.10, sufficient process latitude cannot be obtained.

The weight-average molecular weight of the resin having an acid-decomposable group of the present invention is preferably in the range of 1,000 to 900,000. If it is less than 1,000, the film loss of the unexposed portion after development is large, and if it exceeds 900,000, the developing speed is reduced. Particularly preferred are 2,000-7
It is in the range of 00,000. Here, the weight average molecular weight is defined as a value in terms of polystyrene by gel permeation chromatography.

In the present invention, these alkali-soluble resins having an acid-decomposable group may be used as a mixture of two or more kinds. The amount of the alkali-soluble resin having an acid-decomposable group to be used is 50 to 97% by weight, preferably 60 to 90% by weight, based on the total weight of the resist composition (excluding the solvent). When the use amount of the alkali-soluble resin is less than 50% by weight, dry etching resistance is deteriorated.

The photoacid generator used in the present invention is a compound that generates an acid upon irradiation with actinic rays or radiation.
Examples of the compound used in the present invention that decomposes upon irradiation with actinic rays or radiation to generate an acid include a photoinitiator for photocationic polymerization, a photoinitiator for photoradical polymerization, a photobleaching agent for dyes, and a photochromic Known light (ultraviolet light of 400 to 200 nm, far ultraviolet light, particularly preferably g-ray, h-ray, i-ray, KrF excimer laser light), ArF excimer laser light, electron beam , An X-ray, a molecular beam or an ion beam to generate an acid and a mixture thereof can be appropriately selected and used.

Further, examples of other compounds which generate an acid upon irradiation with actinic rays or radiation used in the present invention include, for example, SI Schlesinger, Photogr. Sci. Eng., 18, 3
87 (1974), TSBetal, Polymer, 21,423 (1980) and the like diazonium salts, U.S. Pat.Nos. 4,069,055 and 4,06
Ammonium salts described in 9,056, Re 27,992, Japanese Patent Application No. 3-140,140, etc., DC Necker et al., Macromolecules, 1
7,2468 (1984), CSWenetal, Teh, Proc.Conf.Rad.Curing
ASIA, p478 Tokyo, Oct (1988), U.S. Pat.No. 4,069,055
No. 4,069,056, etc.
vello etal, Macromorecules, 10 (6), 1307 (1977), Chem.
& Eng.News, Nov. 28, p31 (1988), EP 104,143,
U.S. Patent Nos. 339,049 and 410,201, JP-A-2-150,84
No. 8, iodonium salts described in JP-A-2-296,514 etc.,
JVCrivello etal, Polymer J. 17, 73 (1985), JVCrive
llo etal. J. Org. Chem., 43, 3055 (1978), WRWatt eta
l, J. Polymer Sci., Polymer Chem. Ed., 22, 1789 (1984),
JVCrivello etal, Polymer Bull., 14,279 (1985), JV
Crivello etal, Macromorecules, 14 (5), 1141 (1981), J.
V. Crivello etal, J. PolymerSci., Polymer Chem. Ed., 17,
2877 (1979), European Patent Nos. 370,693 and 3,902,114
233,567, 297,443, 297,442, U.S. Pat.
No. 33,377, No. 161,811, No. 410,201, No. 339,049,
No. 4,760,013, No. 4,734,444, No. 2,833,827, Dokoku Patent No. 2,904,626, No. 3,604,580, No. 3,604,581, etc.
ecules, 10 (6), 1307 (1977), JVCrivello etal, J. Polym
erSci., Polymer Chem. Ed., 17, 1047 (1979), etc., selenonium salts, CSWen et al., Teh, Proc. Conf. Rad.
g Onium salts such as arsonium salts described in ASIA, p478 Tokyo, Oct (1988) and the like, U.S. Pat.No. 3,905,815, JP-B-46
No. 4605, JP-A-48-36281, JP-A-55-32070, JP-A
No. 60-239736, JP-A-61-169835, JP-A-61-169837
No., JP-A-62-58241, JP-A-62-212401, JP-A-63-58241
No. 70243, organic halogen compounds described in JP-A-63-298339, etc., K. Meier et al, J. Rad.Curing, 13 (4), 26 (1986),
TPGill et al, Inorg.Chem., 19,3007 (1980), D. Astru
c, Acc. Chem. Res., 19 (12), 377 (1896), organometallic / organic halides described in JP-A-2-14145, etc., S. Hayase et.
al, J. Polymer Sci., 25, 753 (1987), E. Reichmanis et al.
J.Pholymer Sci., Polymer Chem.Ed., 23, 1 (1985), QQZh
u etal, J. Photochem., 36, 85, 39, 317 (1987), B. Amit eta
l, Tetrahedron Lett., (24) 2205 (1973), DHR Barton eta
l, J. Chem Soc., 3571 (1965), PM Collins et al., J. Chem.
SoC., Perkin I, 1695 (1975), M. Rudinstein et al, Tetrahe
dron Lett., (17), 1445 (1975), JWWalker etal J. Am. Che
m.Soc., 110, 7170 (1988), SCBusman et al., J. Imaging Te
chnol., 11 (4), 191 (1985), HMHoulihan et al, Macormole
cules, 21, 2001 (1988), PM Collins et al., J. Chem. Soc.,
Chem. Commun., 532 (1972), S. Hayase et al, Macromolecule
s, 18, 1799 (1985), E. Reichmanis et al., J. Electrochem. So
c., Solid State Sci. Technol., 130 (6), FMHoulihan et.
al, Macromolcules, 21, 2001 (1988), EP 0290,750
Nos. 046,083, 156,535, 271,851, 0,38
No. 3,343, U.S. Pat.Nos. 3,901,710, 4,181,531, JP-A-60-198538, and a photoacid generator having a 0-nitrobenzyl-type protecting group described in JP-A-53-133022, etc.
etal, Polymer Preprints Japan, 35 (8), G. Berner etal,
J.Rad.Curing, 13 (4), WJMijs etal, Coating Techno
l., 55 (697), 45 (1983), Akzo, H. Adachi et al, Polymer Pr
eprints, Japan, 37 (3), European Patent Nos. 0199,672 and 84515
No. 199,672, No. 044,115, No. 0101,122, U.S. Pat.Nos. 618,564, 4,371,605, 4,431,774, JP-A-64-18143, JP-A-2-245756, Japanese Patent Application No. 3- Compounds which generate sulfonic acid upon photolysis, such as the iminosulfonates described in 140109 and the like, and disulfone compounds described in JP-A-61-166544 and the like can be mentioned.

Further, a group that generates an acid by these lights,
Alternatively, a compound having a compound introduced into the main chain or side chain of a polymer, for example, MEWoodhouse et al., J. Am. Chem.
Soc., 104, 5586 (1982), SPPappas etal, J. Imaging Sc
i., 30 (5), 218 (1986), S. Kondoetal, Makromol.Chem., Rap
id Commun., 9,625 (1988), Y.Yamadaetal, Makromol.Che
m., 152, 153, 163 (1972), JVCrivello etal, J. PolymerS
ci., Polymer Chem. Ed., 17, 3845 (1979), U.S. Pat.
49,137, Dokoku Patent 3914407, JP-A-63-26653, JP-A-55-164824, JP-A-62-69263, JP-A-63-146038
JP-A-63-163452, JP-A-62-153853, JP-A-63-163452
Compounds described in JP-A-146029 can be used.

Further, VNRPillai, Synthesis, (1), 1 (198
0), A. Abad etal, Tetrahedron Lett., (47) 4555 (1971),
Compounds that generate an acid by light described in DHR Barton et al., J. Chem. Soc., (C), 329 (1970), U.S. Pat. No. 3,779,778, and EP 126,712 can also be used.

Among the compounds capable of decomposing upon irradiation with actinic rays or radiation to generate an acid, those which are particularly effectively used are 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).

[0122]

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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.

[0124]

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[0125]

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[0126]

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

[0128]

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Here, the formulas Ar ¹ and Ar ² each independently represent a substituted or unsubstituted aryl group. Preferred substituents include an alkyl group, a haloalkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a nitro group, a carboxyl group, an alkoxycarbonyl group, a hydroxy group, a mercapto group, and a halogen atom.

R ²⁰³ , R ²⁰⁴ and R ²⁰⁵ each independently represent a substituted or unsubstituted alkyl group or aryl group. Preferably, an aryl group having 6 to 14 carbon atoms, 1 to 8 carbon atoms
And substituted derivatives thereof. Preferred substituents are those having 1 to 8 carbon atoms for the aryl group.
And an alkyl group having 1 to 8 carbon atoms, a nitro group, a carboxyl group, a hydroxy group and a halogen atom. The alkyl group is an alkoxy group having 1 to 8 carbon atoms, a carboxyl group or an alkoxycarbonyl group. is there.

[0131] Z ^- represents a counter anion, for example BF ₄ ^{-,
_{AsF 6 -, PF 6 -,}} SbF 6 -, SiF 6 2-, ClO 4 -,
CF ₃ SO ₃ ^-, etc. perfluoroalkane sulfonate anion, pentafluorobenzenesulfonic acid anion, condensed polynuclear aromatic sulfonic acid anion such as naphthalene-1-sulfonic acid anion, anthraquinone sulfonic acid anion, a sulfonic acid group-containing dyes Examples include, but are not limited to:

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

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

[0134]

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[0135]

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[0136]

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[0137]

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[0138]

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[0139]

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[0140]

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[0141]

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[0142]

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[0143]

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[0144]

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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), ALMaycok eta
l, J. Org. Chem., 35, 2532, (1970), E. Goethas et al., Bul
l.Soc.Chem.Belg., 73,546, (1964), HM Leicester, JA
me.Chem.Soc., 51,3587 (1929), JVCrivello etal, J.Po
Chem. Ed., 18,2677 (1980), U.S. Pat. Nos. 2,807,648 and 4,247,473, and JP-A-53-101,331.

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

[0147]

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In the formula, Ar^Three, Ar^FourAre each independently substituted
Or an unsubstituted aryl group. R ²⁰⁶Is replaced or
Indicates an unsubstituted alkyl group or aryl group. A is a substitution
Or unsubstituted alkylene, alkenylene, arylene
Shows a substituent group. Specific examples include the compounds shown below.
However, the present invention is not limited to these.

[0149]

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[0150]

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[0151]

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[0152]

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[0153]

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(4) An o-nitrobenzyl-type photoacid generator represented by the following general formula (PAG7).

[0155]

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[0156]

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[0157]

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[0158]

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[0159]

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[0160]

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[0161]

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In the present invention, the compound that generates an acid upon irradiation with actinic rays or radiation is preferably an onium salt, a disulfone, a 4-position DNQ sulfonic acid ester, a triazine compound, or an o-nitrobenzyl type photoacid generator. .

The amount of the compound capable of decomposing upon irradiation with actinic rays or radiation to generate an acid is usually 0.03% based on the total weight of the photosensitive composition (excluding the coating solvent).
It is used in the range of 0.01 to 40% by weight, preferably 0.0
It is used in an amount of 1 to 20% by weight, more preferably 0.1 to 10% by weight. If the amount of the compound that decomposes upon irradiation with actinic rays or radiation to generate an acid is less than 0.001% by weight, the sensitivity is low, and if the amount is more than 40% by weight, the light absorption of the resist is high. This is not preferable because the profile is deteriorated and the process (especially baking) margin is narrowed.

An organic basic compound can be used in the composition of the present invention. This is preferable because the storage stability is improved and the line width change due to PED is reduced. Preferred organic basic compounds that can be used in the present invention are compounds that are more basic than phenol. Among them, a nitrogen-containing basic compound is preferable. Preferred chemical environments include the structures of the following formulas (A) to (E).

[0165]

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Further preferred compounds are nitrogen-containing basic compounds having two or more nitrogen atoms having different chemical environments in one molecule, and particularly preferred is a ring structure containing a substituted or unsubstituted amino group and a nitrogen atom. Or a compound having an alkylamino group. Preferred specific examples include substituted or unsubstituted guanidine, substituted or unsubstituted aminopyridine, substituted or unsubstituted aminoalkylpyridine, substituted or unsubstituted aminopyrrolidine, substituted or unsubstituted indazol,
Substituted or 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 aminomorpholine, substituted or unsubstituted aminoalkylmorpholine and the like can be mentioned. Preferred substituents are an amino group,
An aminoalkyl group, an alkylamino group, an aminoaryl group, an arylamino group, an alkyl group, an alkoxy group, an acyl group, an acyloxy group, an aryl group, an aryloxy group, a nitro group, a hydroxyl group, and a cyano group. As particularly preferred compounds, guanidine, 1,1-dimethylguanidine, 1,1,3,3-tetramethylguanidine, 2-
Aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-dimethylaminopyridine, 4-dimethylaminopyridine, 2-diethylaminopyridine, 2- (aminomethyl) pyridine, 2-amino-3-methylpyridine, 2-amino -4-methylpyridine, 2-amino-5
-Methylpyridine, 2-amino-6-methylpyridine,
3-aminoethylpyridine, 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,
Examples include, but are not limited to, N-aminomorpholine and N- (2-aminoethyl) morpholine.

These nitrogen-containing basic compounds are used alone or in combination of two or more. The amount of the nitrogen-containing basic compound to be used is generally 0.001-10 parts by weight, preferably 0.01-5 parts by weight, per 100 parts by weight of the photosensitive resin composition (excluding the solvent). If the amount is less than 0.001 part by weight, the above effects cannot be obtained. On the other hand, if it exceeds 10 parts by weight, the sensitivity tends to decrease and the developability of the unexposed part tends to deteriorate.

The chemically amplified positive resist composition of the present invention may further contain, if necessary, a phenolic OH group which promotes solubility in a surfactant, a dye, a pigment, a plasticizer, a photosensitizer and a developer. A compound having two or more compounds can be contained.

Suitable surfactants include, specifically, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether,
Polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether; polyoxyethylene alkyl allyl ethers such as polyoxyethylene octyl phenol ether and polyoxyethylene nonyl phenol ether; polyoxyethylene / polyoxypropylene block copolymers; sorbitan monolaurate ,
Sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate and other sorbitan fatty acid esters, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxy Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as ethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate; EFTOP EF301, EF303;
EF352 (manufactured by Shin-Akita Chemical Co., Ltd.), MegaFac F1
71, F173 (manufactured by Dainippon Ink Co., Ltd.), Flora
Do FC430, FC431 (Sumitomo 3M Limited)
Made), Asahi Guard AG710, Surflon S-38
2, SC101, SC102, SC103, SC10
Fluorinated surfactants such as 4, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.), and organosiloxane polymer KP3
No. 41 (manufactured by Shin-Etsu Chemical Co., Ltd.) or acrylic acid-based or methacrylic acid-based (co) polymerized polyflow No. 41 75, N
o. 95 (manufactured by Kyoeisha Yushi Kagaku Kogyo KK) and the like.

[0170] These surfactants may be added alone or in some combination. A preferable addition amount is 100 parts of the composition (excluding the solvent).
0.0005 to 0.01 parts by weight with respect to parts by weight. Suitable dyes include oily dyes and basic dyes. Specifically, Oil Yellow # 101, Oil Yellow # 103, Oil Pink # 312, Oil Green B
G, Oil Blue BOS, Oil Blue # 603, Oil Black BY, Oil Black BS, Oil Black T-505 (all manufactured by Orient Chemical Industries, Ltd.), Crystal Violet (CI42555), Methyl Violet (CI42535), Rhodamine B (CI45)
170B), malachite green (CI42000),
Methylene blue (CI52015) and the like can be mentioned.

Further, the following spectral sensitizers are added to sensitize the photoacid generator to be used in the wavelength region longer than the deep ultraviolet where the photoacid generator used has no absorption, thereby obtaining the chemically amplified positive resist of the present invention. Can be made sensitive to the i or g line. Examples of suitable spectral sensitizers include benzophenone, p, p'-tetramethyldiaminobenzophenone, p, p'-tetraethylethylaminobenzophenone, 2-chlorothioxanthone, anthrone, 9-ethoxyanthracene, anthracene, and 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.

Examples of the compound having two or more phenolic OH groups that promote solubility in a developing solution include polyhydroxy compounds. Preferably, the polyhydroxy compound includes phenols, resorcin, phloroglucin, phloroglucid, 3,4-trihydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, α, α ′, α ″ -tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene,
Tris (4-hydroxyphenyl) methane, Tris (4
-Hydroxyphenyl) ethane, 1,1′-bis (4-
(Hydroxyphenyl) cyclohexane.

The above chemically amplified positive resist composition is applied onto a substrate (eg, silicon / silicon dioxide coating) used in the manufacture of precision integrated circuit devices by an appropriate application method such as a spinner or a coater, and then applied. A good resist pattern can be obtained by exposing through a mask, baking and developing.

Examples of the developing solution for the chemically amplified positive resist composition of the present invention include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium phosphate, sodium metasilicate, and aqueous ammonia. Primary amines such as ethylamine and n-propylamine, secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, dimethylethanolamine,
Alcoholamines such as triethanolamine, amides such as formamide and acetamide, tetramethylammonium hydroxide, trimethyl (2-hydroxyethyl) ammonium hydroxide, tetraethylammonium hydroxide, tributylmethylammonium hydroxide, and tetraethanolammonium hydroxide , Methyltriethanol ammonium hydroxide,
Quaternary ammonium salts such as benzylmethyldiethanolammonium hydroxide, benzyldimethylethanolammonium hydroxide, benzyltriethanolammonium hydroxide, tetrapropylammonium hydroxide and tetrabutylammonium hydroxide, and alkalis such as cyclic amines such as pyrrole and piperidine And the like.

[0175]

EXAMPLES Examples of the present invention will be shown below, but the present invention is not limited to these examples. In addition,% shows weight% unless otherwise specified. Synthesis Example of Polymer Type Dissolution Inhibitor [Synthesis Example 1 of Polymer] 21 g of parahydroxystyrene, 5.8 g of t-butyl vinyl ether, and 0.1 g of t-butyl vinyl ether.
86 g of 2,2-bis (4-hydroxycyclohexyl) propane was dissolved in 100 ml of THF, and p-
Add 0.005 g of toluenesulfonic acid, and add
Stirred for hours. The reaction solution was poured into 3 liters of water, and the precipitated powder was collected by filtration and dried to obtain the desired product (weight average molecular weight of 4).
5,000). The protection rate was 30%.

[Synthesis Example 2 of Polymer] 50 g of polyparahydroxystyrene (water content: 1.1%) and 4 g of 2,2-bis (4-hydroxycyclohexyl) propane were put in a flask, and dissolved in THF. 17 g of vinyl ether and 10 mg of paratoluenesulfonic acid were added, and the mixture was stirred at room temperature for 16 hours. After adding 20 mg of triethylamine to the reaction mixture, the mixture was poured into water, and the precipitate was collected by filtration.
Drying gave 55 g as a white powder.

Synthesis Example of Non-polymeric Dissolution Inhibitor Synthesis Example 1 of Dissolution Inhibitor Dissolution inhibitor 1 having the following structure was synthesized in the same manner as in the synthesis example of the non-polymeric dissolution inhibitor described in JP-A-7-271037. .

[0178]

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Synthesis Example 2 of dissolution inhibitor In the same manner as in Synthesis Example 1 of dissolution inhibitor, dissolution inhibitor 2 having the following structure was synthesized.

[0180]

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Synthesis Example of Photoacid Generator 45% aqueous solution of triphenylsulfonium Cl salt
9 g (0.030 mol) was dissolved in 200 ml of ion-exchanged water. Dodecylbenzenesulfonic acid Na salt 1 was added to this solution.
A solution of 0.5 g (0.030 mol) of 400 ml of ion-exchanged water was added with stirring at room temperature. The precipitated viscous solid was separated by decanting, and washed with 1 L of ion-exchanged water. The obtained viscous solid was dissolved in 100 ml of acetone and poured into 500 ml of ion-exchanged water with stirring to cause recrystallization. 14. The precipitate was dried at 50 ° C. under vacuum, resulting in a glassy solid.
5 g were obtained.

Example 1 100 parts by weight of the polymer synthesized in Synthesis Example 1 of the polymer, 5.3 parts by weight of the photoacid generator synthesized in the synthesis example of the photoacid generator, 0,2,4,5-triphenylimidazole .32
Parts by weight, fluorinated surfactant "Fluorard FC-43"
0 "(Fluorochemical-manufactured by Sumitomo 3M Co., Ltd.) in an amount of 0.2 parts by weight to 3-methoxy-3-methylbutyl acetate 550
It was dissolved in parts by weight and filtered using a polytetrafluoroethylene microfilter having a pore size of 0.20 μm to prepare a resist solution. The resist solution was applied on a 6-inch silicon wafer using a coating machine CDR-650 manufactured by Canon Inc.
After drying at 60 ° C. for 60 seconds, a resist film having a thickness of 0.760 μm was obtained. The surface of the resist film was observed with an optical microscope, but no residue was found and no striation was observed. When the film thickness of the resist was measured at 54 points using an Alpha Step-100 (manufactured by TENVCOR), the dispersion of the measured values was 28 °.
Met.

Further, the prepared resist solution was kept at a constant temperature of 5 ° C. for one month, and a time-dependent test for generation of precipitates was carried out (storage stability test I). The sediment in the aging test was confirmed by measuring the fine particles in the resist solution with an automatic fine particle measuring machine (KL manufactured by Lion).
-21 type). The number of particles having a size of 0.30 μm or more before cooling and storage was 6 / mL, and after cooling and storage was 10 / mL. Furthermore, the resist solution was left at 25 ° C. for 2 months, and the KrF excimer stepper (Nikon NSR) was used.
Exposure using -1505EX, NA 0.42) and 2.3
After developing with 8 wt% TMAH for 60 seconds and rinsing for 20 seconds, the resist sensitivity was measured (storage stability test II), and compared with that immediately after preparation, the difference in sensitivity was 1% or less.

On the other hand, the prepared resist solution was transferred to a 150 mL beaker, allowed to stand at 25 ° C. in an open state for 24 hours, and the water content was determined by a Karl Fischer measuring instrument. 0.1% by weight immediately after preparation and 0.20% after 24 hours
% By weight, indicating low hygroscopicity. This resist was applied by a spin coater and baked at 120 ° C. for 60 seconds to form a 0.76 μm film. This film is
F Excimer Laser Stepper (NSR1505EX: N
A0.42), baked at 110 ° C. for 60 seconds, developed with a 2.38% aqueous solution of tetramethylammonium hydroxide for 60 seconds, rinsed with pure water for 20 seconds, and formed a pattern. The wafer on which the 1 μm pattern is formed is placed on a hot plate at a temperature for heat resistance evaluation for 2 minutes, and then the pattern sag is observed with a scanning electron microscope. If the side wall angle of the pattern is 50 ° or more, the heat resistance test is passed. The maximum temperature at which the side wall angle became 50 degrees or more was evaluated as heat resistance. The heat resistance of the resist of Example 1 was higher by 10 ° C. than that of Comparative Example 2 described later.

Example 2 A resist solution was prepared and evaluated in the same manner as in Example 1 except that the polymer synthesized in Polymer Synthesis Example 2 was used instead of the polymer of Example 1. The variance of the measured film thickness was 25 °. In the storage stability test I, the number of particles of 0.30 μm or more in the resist solution before the cold storage was 6 / mL, and after the cold storage was 10 / mL. In the storage stability test II, the difference in sensitivity was 1% or less. Moisture content immediately after preparation is 0.1 wt%, and after 24 hours is 0.2 wt%.
wt%, indicating low hygroscopicity.

Example 3 100 parts by weight of the polymer synthesized in Synthesis Example 1 of the polymer, 20 parts by weight of dissolution inhibitor 1 synthesized in the synthesis example of the non-polymer type dissolution inhibitor, 10 parts by weight of dissolution inhibitor 2 8 parts by weight of the photoacid generator synthesized in the synthesis example of the photoacid generator, 2,
0.6 parts by weight of 4,5-triphenylimidazole, 0.2 parts by weight of a fluorosurfactant "Fluorad FC-430" (Fluorochemical, manufactured by Sumitomo 3M), and 780 parts by weight of 3-methoxy-3-methylbutyl acetate And filtered using a polytetrafluoroethylene microfilter having a pore size of 0.20 μm to prepare a resist solution. This resist solution was evaluated in the same manner as in Example 1.

The dispersion of the measured film thickness was 20 °. In the storage stability test I, the number of particles having a size of 0.30 μm or more in the resist solution before the cooling and storage was 7 / ml, and after the cooling and storage was 12 / ml. In storage stability test II,
The difference in sensitivity was 1% or less. The water content immediately after preparation is 0.1
It was 5 wt%, and after 24 hours, 0.2 wt%, indicating that the hygroscopicity was low. The resist was applied by a spin coater and baked at 120 ° C. for 60 seconds.
A 76 μm film was formed. This film was exposed with a KrF excimer laser stepper (NSR1505EX; NA 0.42) and baked (PEB) at 110 ° C. for 60 seconds.
The pattern was formed by developing with a 2.38% aqueous solution of tetramethylammonium hydroxide for 60 seconds and rinsing with pure water for 20 seconds. When there is no aging (PED) from exposure to PEB, and when the PED is 1 hour, 0.
When comparing 35 μm patterns at the same exposure dose,
There was no difference between the pattern width and the profile, and it was good.

Examples 4 to 8 and Comparative Examples 1 to 4 Instead of 3-methoxy-3-methylbutyl acetate used in Example 3, the solvents shown in Table 1 below were used, and the other conditions were the same as in Example 3. Then, a resist solution was prepared and evaluated in the same manner as in Example 1. Table 2 shows the results.

[0189]

[Table 1]

[0190]

[Table 2]

[0191]

Industrial Applicability The chemically amplified positive photoresist composition of the present invention is excellent in storage stability and solubility of each component, and is excellent in uniformity of coating without troubles such as uncoating and striation. Further, the storage stability of the solution is excellent, the precipitation or decomposition of the fine particles of the photosensitive agent does not occur during the storage, and the solution has excellent hygroscopicity, sensitivity, resolution, heat resistance and resist shape.

Claims (6)

[Claims] (1) a compound having a group which decomposes under the action of an acid to increase solubility in an alkaline developer;
A positive photoresist composition comprising (b) a compound which generates an acid upon irradiation with actinic rays or radiation, and (c) alkoxybutyl acetate and / or alkoxypentyl acetate. 2. The method according to claim 1, wherein the alkoxybutyl acetate is 3-methoxybutyl acetate.
The positive photoresist composition as described in the above. 3. The positive photoresist composition according to claim 1, wherein (c) is alkoxyalkyl butyl acetate and / or alkoxyalkyl pentyl acetate. 4. The positive photoresist composition according to claim 3, wherein the alkoxyalkyl butyl acetate contains 3-methoxy-3-methylbutyl acetate. 5. The method according to claim 1, wherein (a) is decomposed by the action of an acid,
It is a polymer type compound having a group that increases solubility in an alkaline developer and / or a non-polymer type compound having a group that decomposes under the action of an acid to increase solubility in an alkaline developer. The positive photoresist composition according to claim 1, wherein 6. The group (a) which is decomposed by the action of an acid to increase the solubility in an alkali developer, is selected from tertiary alkyl ester groups and tertiary alkyl carbonate groups. One and / or at least one selected from an acetal group and a silyl ether group
The positive photoresist composition of claim 1, comprising a seed.