JP2002006494A - Positive resist laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a positive resist laminate adaptable to exposure in the far ultraviolet region, having high resolving power, nearly free of line waves and development defects particularly in the case of a narrow line/space of <=0.2 μm and having high suitability to production. SOLUTION: The positive resist laminate has a first resist layer on a substrate and a second resist layer on the first resist layer, the first resist layer contains (A-1) a polymer containing both repeating units of formula (1) and repeating units of formula (2) and the second resist layer contains (B) a polysiloxane or polysilsesquioxane having a group which can be decomposed by an acid and having solubility in an alkali developing solution increased by the action of the acid and (C) a compound which generates the acid when irradiated with active light or radiation.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positive type silicone-containing resist laminate for exposure to radiation such as ultraviolet rays, far ultraviolet rays, X-rays, electron beams, molecular beams, gamma rays and synchrotron radiation. Is used in the manufacturing process of semiconductors such as ICs, for example, when manufacturing circuit boards, etc., which contains a positive type silicone for micromachining, which provides particularly high resolution and sensitivity, a rectangular solid resist and has a wide process tolerance. It relates to a resist laminate.

[0002]

2. Description of the Related Art The resolution limit of conventional single-layer resists has become evident with the increasing integration of LSIs. By forming resists in multiple layers instead of single layers, thick and fine high-profile ratio patterns can be formed. Methods of forming have been proposed.
That is, a thick organic polymer film is formed on the first layer, a thin resist material layer is formed on the second layer thereon, and then the second resist material is irradiated with high energy rays and developed. The first organic polymer is anisotropically etched by oxygen plasma etching (O ₂ RIE) using the resulting pattern as a mask to obtain a pattern having a high rectangular shape (phosphorus, solid state technology). Vol. 24, p. 73 (1981)).

In this case, the second resist layer is made of O ₂ -R
Silicon-containing polymers are commonly used because of their high IE resistance. In particular, many attempts have been made to use an acid-decomposable group-containing polysiloxane or polysilsesquioxane having a silicon atom in the polymer main chain in order to increase the silicon content. For example, JP-A-63-
No. 218948, JP-A-4-245248, 6-1.
Nos. 84311, 8-160620 and JP-A-9-27
No. 4319 and the like. The first resist layer is made of a novolak resin or the like in order to impart adhesion and film forming properties to the substrate, high dry etching resistance, immiscibility with the second resist layer, high light absorption characteristics at the exposure wavelength, and the like. Is generally and widely used.

However, this method has poor adhesion to a second resist layer using polysiloxane or polysilsesquioxane, and is therefore particularly disadvantageous when used for forming fine lines / spaces of 0.2 μm or less. However, there is a problem that the line is easily undulated and the pattern is likely to collapse. Further, in the first resist layer containing the novolak resin, it is necessary to perform a high-temperature treatment for a long time, and there is a problem that the suitability for production is extremely low in the production of semiconductor devices and the like. If the high-temperature treatment is performed in a short time, the solidification of the first resist layer becomes insufficient, and a phenomenon (intermix) of mixing with the second resist layer occurs. As a result, there is also a problem that a pattern with a large development residue is formed. .

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a positive resist laminate having a high resolving power and capable of coping with exposure in the far ultraviolet region in the manufacture of semiconductor devices. Another object of the present invention is to provide a positive resist laminate which provides a resist pattern with less line waviness particularly in a fine line / space of 0.2 μm or less. Another object of the present invention is to provide, among other things, 0.1.
An object of the present invention is to provide a positive resist laminate having a small amount of development residue in a fine line / space of 2 μm or less. Another object of the present invention is to provide a positive resist laminate having high manufacturing suitability.

[0006]

Means for Solving the Problems The inventors of the present invention have made intensive studies while paying attention to the above characteristics, and as a result, have completed the present invention. That is, the object of the present invention can be achieved by the following configurations.

(1) A two-layer resist having a first resist layer on a substrate and a second resist layer on the first resist layer,
The first resist layer contains (A-1) a polymer containing both a repeating unit represented by the following general formula (1) and a repeating unit represented by the following general formula (2). (B) a polysiloxane or polysilsesquioxane having a group decomposable by an acid and having a property of increasing the solubility in an alkaline developer by the action of an acid;
And (C) a compound capable of generating an acid upon irradiation with actinic rays or radiation.

[0008]

Embedded image

In the formula, Y ¹ represents a hydrogen atom, an alkyl group, a cyano group or a halogen atom, L ¹ represents a divalent linking group which may have a substituent, and J represents a substituent. Represents an alicyclic hydrocarbon group which may be substituted. a1 represents 0 or 1.
Y ² has the same meaning as Y ¹ , and L ² has the same meaning as L ¹ . K represents an aryl group which may have a substituent. a2 and a3 each independently represent 0 or 1.

(2) Used in the first resist layer (A-
1) The component polymer has a hydroxyl group,
The first resist layer contains at least one group selected from a primary amino group and a secondary amino group, and the first resist layer further comprises (A-
2) It is characterized by containing a crosslinking agent activated by an acid and capable of forming a crosslinked structure by reacting with the polymer of the component (A-1), and (A-3) a compound capable of generating an acid by heat. The positive resist laminate according to the above (1).

(3) (B) a polysiloxane or a polysilsesquicene having a group decomposable by an acid contained in the second resist layer and having a property of increasing the solubility in an alkaline developer by the action of an acid. The positive resist laminate according to the above (1) or (2), wherein the oxane has a structure represented by the following general formula (3) in a side chain.

[0012]

Embedded image

In the formula, J ¹ represents an alkylene group which may have a substituent, and J ² represents an arylene group which may have a substituent or an alicyclic group which may have a substituent. It represents group, or an optionally bridged alicyclic group which may have a substituent group, J ³
Represents a divalent linking group, J ⁴ represents a divalent to tetravalent linking group, and G represents a group decomposed by the action of an acid. k, l,
m and n each independently represent 0 or 1. Where k, l,
m and n are not all 0 at the same time. p is 1 to
Represents an integer of 3.

(4) The above (1), wherein the second resist layer further comprises (D) a nitrogen-containing basic compound.
The positive resist laminate according to any one of (1) to (3). (5) The positive resist laminate according to any one of (1) to (4) above, wherein the second resist layer further contains (E) a fluorine-based and / or silicon-based surfactant. .

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail, but the present invention is not limited thereto. The positive resist laminate of the present invention comprises a first resist layer containing a polymer containing a repeating unit represented by the general formula (1) and a repeating unit represented by the general formula (2), which is a component (A-1); And a second resist layer containing a polymer having a silicon atom in the main chain as a component and being water-insoluble and soluble in an aqueous alkali solution by the action of an acid.

In order to achieve the object of the present invention to a higher degree, in the polymer (A-1) contained in the first resist layer, the content of the repeating unit represented by the general formula (1) is 10 ９０90 mol%, preferably 20-8.
0 mol% is more preferable, and 25 to 75 mol%.
Is particularly preferred. The content of the repeating unit represented by the general formula (2) is preferably 10 to 90 mol%, more preferably 20 to 80 mol%, and more preferably 2 to 80 mol%.
It is particularly preferred that it is 5 to 75 mol%.

In the general formula (1), Y ¹ is preferably a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a cyano group, a halogen atom (Cl, Br, I, etc.), more preferably a hydrogen atom, a carbon atom It is an alkyl group of the formulas 1 to 3, particularly preferably a hydrogen atom and a methyl group.

L ¹ represents a divalent linking group, and is preferably an alkylene group, an arylene group, or an aralkylene group. These groups may have a substituent, and examples of the substituent include a halogen atom such as Cl, Br, and F;
CN group, -OH group, amino group, -NH (R ⁹ )-group (where R ⁹ represents an alkyl group having 1 to 4 carbon atoms), an alkyl group having 1 to 4 carbon atoms, and 3 to 8 carbon atoms , An aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 14 carbon atoms, and the like. L ¹ is more preferably an alkylene group having 1 to 8 carbon atoms which may have a substituent, a phenylene group, an aralkylene group having 7 to 10 carbon atoms, and 2 carbon atoms which may have a substituent. To 6 alkylene groups and phenylene groups are particularly preferred.

J is preferably a cycloalkyl group having 3 to 8 carbon atoms or a bridged hydrocarbon group having 4 to 30 carbon atoms. These groups may have a substituent group include the substituents mentioned in the description of the L ¹ examples of the substituent groups. J is more preferably a bridged alicyclic hydrocarbon group having 5 to 25 carbon atoms, and preferable examples are given below.

[0020]

Embedded image

[0021]

Embedded image

Among these groups, particularly preferred examples are (5), (6), (7), (8), (9), (1)
0), (13), (14), (15), (23), (2)
8), (36), (37), (40), (42), (4)
7). a1 represents 0 or 1.

In the general formula (2), Y ² has the same meaning as Y ¹ , and L ² has the same meaning as L ¹ . K is preferably an aryl group having 6 to 20 carbon atoms which may have a substituent, examples of the substituent may include the substituents described in the explanation of the above L ^1. K is more preferably an aryl group having 6 to 15 carbon atoms which may have a substituent, and particularly preferably a phenyl group, a naphthyl group, an anthryl group, and a phenanthryl group which may have a substituent. . a2 and a3 each independently represent 0 or 1.

In the general formulas (1) and (2), L
^At least one of the groups represented by ¹ , L ² , J, and K is a hydroxyl group, an amino group, —NH
It preferably has a (R ⁹ ) -group (where R ⁹ represents an alkyl group having 1 to 4 carbon atoms), and a hydroxyl group is particularly preferable.

The polymer (A-1) used in the present invention has the object of improving film-forming properties, adhesion, developability, etc. in addition to the repeating units represented by the general formulas (1) and (2). And a copolymer containing another repeating unit. Examples of the monomer corresponding to such another repeating unit include, for example, an addition-polymerizable monomer selected from acrylates, methacrylates, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, and the like. Compounds having one saturated bond are exemplified.

Specifically, for example, acrylic esters such as alkyl (the alkyl group has 1 to 1 carbon atoms)
Acrylates (for example, methyl acrylate, ethyl acrylate, propyl acrylate, amyl acrylate, cyclohexyl acrylate, ethylhexyl acrylate, octyl acrylate, acrylate-
t-octyl, chloroethyl acrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, benzyl acrylate, methoxybenzyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, etc.);

Methacrylic esters such as alkyl (alkyl having preferably 1 to 10 carbon atoms) methacrylate (eg, methyl methacrylate,
Ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate,
Benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, etc.);

Acrylamides, for example, acrylamide, N-alkylacrylamide (alkyl groups having 1 to 10 carbon atoms, for example, methyl, ethyl, propyl, butyl, t-butyl, heptyl, octyl) , Cyclohexyl group, hydroxyethyl group, etc.), N, N-dialkylacrylamide (alkyl group having 1 to 10 carbon atoms, for example, methyl group, ethyl group, butyl group, isobutyl group, ethylhexyl group, cyclohexyl) Groups, etc.), N-hydroxyethyl-N-methylacrylamide, N-2-
Acetamidoethyl-N-acetylacrylamide and the like;
Methacrylamides, for example, methacrylamide, N-alkyl methacrylamide (an alkyl group having 1 to 10 carbon atoms, for example, a methyl group, an ethyl group, a t-butyl group, an ethylhexyl group, a hydroxyethyl group, a cyclohexyl group, etc. ), N, N-dialkylmethacrylamide (alkyl groups include ethyl, propyl, butyl, etc.), N-hydroxyethyl-N
-Methyl methacrylamide and the like;

Allyl compounds such as allyl esters (eg, allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate, etc.), allyloxy Ethanol, etc .;

Vinyl ethers such as alkyl vinyl ethers (eg, hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethyl Butyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether, etc.);

Vinyl esters such as vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxy acetate, vinyl butoxy acetate, Vinyl acetoacetate, vinyl lactate, vinyl-β-phenylbutyrate, vinylcyclohexylcarboxylate and the like;

Dialkyl itaconates (eg, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, etc.); dialkyl esters of fumaric acid (eg, dibutyl fumarate, etc.) or monoalkyl esters; acrylic acid, methacrylic acid, crotonic acid , Itaconic acid, maleic anhydride, maleimide, acrylonitrile, methacrylonitrile, maleilenitrile and the like. In addition,
Any addition-polymerizable unsaturated compound copolymerizable with the above-mentioned various repeating units may be used.

The weight average molecular weight of the polymer (A-1) used in the present invention is not particularly limited, but is preferably from 1,000 to 1,000,000, more preferably from 2,000 to 100,000, from the viewpoint of organic solvent properties and film forming properties. preferable. Specific examples of the polymer (A-1) used in the present invention include the following, but are not limited thereto. The number attached to the arc is the mole fraction. Hereinafter, specific examples of the polymer (A-1) used in the first resist layer will be described.

[0034]

Embedded image

[0035]

Embedded image

In the first resist layer, in order to achieve a higher purpose, the first resist layer is activated with (A-2) acid,
A thermal crosslinking agent capable of reacting with a polymer containing a repeating unit represented by the general formula (2) to form a crosslinked structure (also referred to as a “thermal crosslinking agent”); (A thermal acid generator).

As the thermal crosslinking agent (A-2), known compounds can be widely used. For example, the thermal crosslinking agent (A-2) is substituted with at least one group selected from a methylol group, an alkoxymethyl group and an acyloxymethyl group. Melamine compounds, benzoguanamine compounds, glycoluril compounds or urea compounds are preferred. Examples of the alkoxymethyl group include methoxymethyl, ethoxymethyl, propoxymethyl, butoxymethyl and the like. Examples of the acyloxymethyl group include acetyloxymethyl and the like. The number of methylol groups, alkoxymethyl groups, and acyloxymethyl groups contained in these compounds is
In the case of melamine, the number is 2 to 6, preferably 5 to 6, and in the case of a glycoluril compound or a benzoguanamine compound, the number is 2 to 4, preferably 3 to 4. In the case of a urea compound, the number is 3 to 4. Among these, hexamethoxymethylmelamine, tetramethoxymethylbenzoguanamine, and tetramethoxymethylglycoluril compounds are most preferable from the viewpoints of thermal crosslinkability and storage stability.

All of the above methylol group-containing compounds can be obtained by reacting melamine, guanamine or urea with formalin in the presence of a basic catalyst such as sodium hydroxide, potassium hydroxide, ammonia and tetraalkylammonium hydroxide.

The compound having an alkoxymethyl group is
It can be obtained by heating the above methylol group-containing compound in alcohol in the presence of an acid catalyst such as hydrochloric acid, sulfuric acid, nitric acid, methanesulfonic acid and the like. The acyloxymethyl group-containing compound is obtained by reacting the methylol group-containing compound with an acid anhydride or an acid halide in the presence of a base catalyst. The content of the thermal crosslinking agent in the resist composition of the first resist layer of the present invention is 2 to 50% by weight in terms of solid content.
And more preferably 5 to 30% by weight.

As the thermal acid generator (A-3), the temperature at which the acid starts to be generated is 150 to 220 ° C., and more preferably 170 to 220 ° C.
The temperature is preferably 200 ° C., and a sulfonic acid ester compound or a diaryliodonium salt is preferably used. The sulfonic acid ester compound is preferably an organic sulfonic acid ester having 3 to 20 carbon atoms, specifically, a sulfonic acid ester of a secondary alcohol such as 2-propanol, 2-butanol, 2-pentanol or cyclohexanol. Is preferred. As the diaryliodonium salt compound, a diaryliodonium cation,
Anions of organic sulfonic acids, SbF ₆ anions, salts with PF ₆ anion or AsF ₆ anion.
Here, the anion of an organic sulfonic acid is preferable as the anion. Specific examples of the diaryliodonium salt compound include the following compounds.

[0041]

Embedded image

[0042]

Embedded image

[0043]

Embedded image

[0044]

Embedded image

Of these, salts of diaryliodonium and organic sulfonic acids are preferred from the viewpoints of stability and solvent solubility. Among them, the aryl group has 1 to 12 carbon atoms.
A salt of a diaryliodonium cation having a straight-chain or branched alkyl group or an alkoxy group having 1 to 12 carbon atoms as a substituent with an organic sulfonic acid anion is preferred from the viewpoint of safety. Here, as a linear or branched alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec -Butyl group, i-butyl group, t-butyl group, n-amyl group, i-amyl group, t-
Amyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-decyl, n-dodecyl, cyclopropyl, cyclopentyl, cyclohexyl, methoxy, ethoxy, propoxy And butoxy groups. Examples of the aryl group include a phenyl group, a naphthyl group, an anthryl group, and a phenanthryl group.

Examples of the organic sulfonic acid anion include trifluoromethanesulfonate, methanesulfonate, a straight-chain or branched alkyl group having 1 to 12 carbon atoms and an alkoxy group having 1 to 12 carbon atoms on the aryl group (these alkyl groups). Examples of the group and the alkoxy group are the same as those described above.) Or an arylsulfonate which may have a halogen atom as a substituent is preferred from the viewpoint of solvent solubility. Examples of the aryl group include the same as those described above. These thermal acid generators can be used alone or in combination of two or more. The thermal acid generator is usually 0.5 to 0.5 parts by weight based on 100 parts by weight of the resist composition of the first resist layer.
10 parts by weight, preferably 1 to 5 parts by weight.

The first resist layer used in the present invention includes:
(A-1) a polymer described above, (A-2) a thermal crosslinking agent,
(A-3) In addition to the thermal acid generator, other polymers may be added in order to improve the film forming property, heat resistance, dry etching resistance and the like. Preferred examples of such polymers include novolak phenolic resins, specifically phenolaldehyde resins, o-cresol formaldehyde resins, p-cresol formaldehyde resins, xylenol formaldehyde resins, or co-condensates thereof. . Further, as described in JP-A-50-125806, phenol or cresol substituted with an alkyl group having 3 to 8 carbon atoms, such as t-butylphenol aldehyde resin, together with the phenol resin as described above. A condensate with formaldehyde may be used in combination. Also, a polymer having a phenolic hydroxy group-containing monomer such as N- (4-hydroxyphenyl) methacrylamide as a copolymer component, p-hydroxystyrene, o-hydroxystyrene, m-isopropenylphenol, p-isopropenylphenol And the like, or a homo- or copolymerized polymer, or a polymer in which these polymers are partially etherified or partially esterified.

The first resist composition of the present invention may contain, if necessary, JP-A-4-122938 and JP-A-2-27.
You may add the aromatic polyhydroxy compound of 5955, 4-230754, etc. The first resist composition of the present invention may contain an organic basic compound.

Solvents for dissolving the components (A-1), (A-2) and (A-3) in the first resist composition of the present invention include ketones such as methyl ethyl ketone and cyclohexanone, ethylene glycol monomethyl ether,
Alcohol ethers such as ethylene glycol monoethyl ether, dioxane, ethers such as ethylene glycol dimethyl ether, methyl cellosolve acetate, cellosolve esters such as ethyl cellosolve acetate, butyl acetate, methyl lactate, fatty acid esters such as ethyl lactate, 1, Examples thereof include halogenated hydrocarbons such as 1,2-trichloroethylene, and highly polar solvents such as dimethylacetamide, N-methylpyrrolidone, dimethylformamide, and dimethylsulfoxide. These solvents can be used alone or as a mixture of a plurality of solvents.

The first resist composition of the present invention may optionally contain a dye, a plasticizer, an adhesion aid, a surfactant and the like. If the specific example is given, methyl violet, crystal violet, dye such as malachite green, stearic acid, acetal resin, phenoxy resin, alkyd resin, plasticizer such as epoxy resin,
There are adhesion aids such as hexamethyldisilazane and chloromethylsilane, and surfactants such as nonylphenoxypoly (ethyleneoxy) ethanol and octylphenoxypoly (ethyleneoxy) ethanol. Especially in dyes,
Dyes containing an alkali-soluble group such as an aromatic hydroxyl group or a carboxylic acid group in the molecule, such as glutamine, are particularly advantageously used.

Next, the second resist layer will be described. Second
The polymer of the component (B) used in the resist layer will be described. Examples of the polysiloxane or polysilsesquioxane as the component (B) include those having a group decomposable by an acid in a side chain, and preferably those having a structure represented by the general formula (3) in the side chain. It is. Thereby, the resist performance such as the resolution and the heat resistance are excellent.

In the general formula (3), J ¹ is preferably an alkylene group having 1 to 10 carbon atoms which may have a substituent.
And the same as the examples of the substituent of L ^{1 in} the above. J ¹ is preferably an alkylene group having 1 to 6 carbon atoms, and more preferably an alkylene group having 1 to 4 carbon atoms (such as a methylene group, an ethylene group, and a propylene group). k represents 0 or 1. J ² is an arylene group having 6 to 14 carbon atoms which may have a substituent, a cycloalkylene group having 3 to 8 carbon atoms which may have a substituent,
Alternatively, it is preferably a bridged alicyclic group having 5 to 30 carbon atoms which may have a substituent. Examples of the substituent include J
^This is the same as described in ¹ . More preferably, J ² is an arylene group having 6 to 10 carbon atoms (such as a phenylene group or a naphthylene group), a cycloalkylene group having 5 to 8 carbon atoms (such as a cyclohexylene group or a cyclooctylene group), or a general formula (1) This is a linking group having the same structure as the bridged alicyclic group described in the description of (1).

Particularly preferably, J ² is a phenylene group, a cycloalkylene group having 6 to 8 carbon atoms (cyclohexylene group, cyclooctylene group, etc.), and among the above-mentioned bridged alicyclic groups, (5), (6), (7), (8), (9),
(10), (13), (14), (15), (23),
(28), (36), (37), (40), (42),
It is a linking group represented by (47). l represents 0 or 1.

J ³ represents a divalent linking group, -O-, -N
(R ²¹ )-, -COO-, -OC (= O)-, -O (C
= O) O -, - CON (R 21) -, - N (R 21) CO
—, —NH—CO—NH— group and the like. R ²¹ has the same meaning as R ⁹ in formula (1). J ³ is preferably -COO-, -OCO-, -O-, -CON (R
^{21) -, - N (R} 21) is CO-. m represents 0 or 1.

J ⁴ represents a divalent to tetravalent linking group, having 1 carbon atom
-8 alkylene group, cycloalkylene group having 4-10 carbon atoms, bridged alicyclic group having 5-30 carbon atoms, 6-1 carbon atoms
2 arylene groups are preferred, and more preferably 1 carbon atom.
To 5 divalent or trivalent alkylene group, 6 to 8 carbon atoms
A divalent or trivalent cycloalkylene group, or a divalent to tetravalent phenylene group; n represents 0 or 1.

G represents an acid-decomposable group, and —C (＝ O) —O
—R ³¹ , —OC (＝ O) —O—R ³¹ , —O—CH (CH
₃₎ -O-R ³² or -COOCH (CH ₃₎ is preferably a -O-R ^32. Here, R ³¹ represents a tertiary alkyl group, preferably a tertiary alkyl group having 4 to 8 carbon atoms (t-butyl group, t-amyl group, etc.). R ³² represents an optionally substituted alkyl group having 2 to 12 carbon atoms or an aralkyl group. As an example of the substituent, the general formula (1)
And the same as the examples of the substituent of L ^{1 in} the above. R ³² is preferably an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, t
-Butyl group, isoamyl group, cyclohexylmethyl group,
Cyclohexylethyl group, benzyl group, phenethyl group,
And a phenyloxyethyl group. p represents an integer of 1 to 3. In the general formula (3), k, l, m, and n are not simultaneously 0.

The polysiloxane or polysilsesquioxane of the component (B) is selected from the compounds represented by the above general formula (3) from the viewpoint of controlling heat resistance, solubility, film forming property and the like and improving lithography performance.
The polymer may have one or a plurality of structures represented by Further, for the same reason, it is preferable that a part of G is a —OH group or a —COOH group. In this case, G
Is preferably a molar fraction of 0 to 60%, more preferably 2 to 40%.

For the purpose of improving lithography performance, film forming property and heat resistance, it is preferable to introduce a side chain represented by the following general formulas (4) and / or (5).

[0059]

Embedded image

In the formula, J ⁵ and J ⁶ have the same meanings as J ¹ and J ² respectively. q and r each independently represent 0 or 1. A
Represents an alkyl group, a cycloalkyl group, a bridged alicyclic group, an aryl group or an aralkyl group, each of which may have a substituent. Examples of the substituent include those represented by the above general formula (1)
And the same substituents as those described above for L ¹ can be mentioned. A is preferably an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, and 5 to 30 carbon atoms.
A bridged alicyclic group, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, and more preferably an alkyl group having 1 to 8 carbon atoms (a methyl group, an ethyl group, a propyl group). , Cyclohexylmethyl group, etc.), a cycloalkyl group having 6 to 8 carbon atoms (cyclohexyl group, cyclooctyl group, etc.), among the bridged alicyclic groups described in the description of the general formula (1), (5), (6), (7), (8), (9), (1)
0), (13), (14), (15), (23), (2)
8), (36), (37), (40), (42), (4)
7), aryl groups having 6 to 9 carbon atoms (such as phenyl group and p-methylphenyl group), and aralkyl groups having 7 to 10 carbon atoms (such as benzyl group and phenethyl group).

J ⁷ has the same meaning as J ¹ . R ⁴¹ and R ⁴² are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. R ⁴¹ and R ⁴² may combine with each other to form a ring. In this case, the number of rings is preferably 1 to 3, and more preferably those having the following structures.

[0062]

Embedded image

The proportion of the repeating units represented by the general formulas (4) and / or (5) is preferably from 0 to 70%, more preferably from 0 to 70% by mole fraction in the polymer.
It is 60%, particularly preferably 0 to 50%.

The weight-average molecular weight of the acid-decomposable group-containing polysiloxane and polysilsesquioxane of the component (B) contained in the second resist layer of the present invention is not particularly limited. In view of the balance of solubility, organic solvent solubility, performance, and the like, it is preferably 1,000 to 100,000,
500-50,000 is preferred.

Examples of the polysiloxane and the polysilsesquioxane as the component (B) contained in the second resist layer used in the present invention are shown below, but are not limited thereto.

[0066]

Embedded image

[0067]

Embedded image

Next, the compound (C) which generates an acid upon irradiation with actinic rays or radiation will be described. The (C) photoacid generator used in the present invention is a compound that generates an acid upon irradiation with actinic rays or radiation. The photoacid generator (C) used in the present invention includes a photoinitiator for photocationic polymerization, a photoinitiator for photoradical polymerization, a photodecolorant for dyes, a photochromic agent, and a microresist. Known light (ultraviolet light of 400 to 200 nm, far ultraviolet light, particularly preferably g-line, h-line, i-line, K-line).
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 (C) used in the present invention include, for example, onium salts such as diazonium salts, ammonium salts, phosphonium salts, iodonium salts, sulfonium salts, selenonium salts and arsonium salts, and organic halogens. Compounds, organometallic / organic halides, photoacid generators having o-nitrobenzyl-type protecting groups,
Examples thereof include compounds that generate sulfonic acid upon photodecomposition represented by iminosulfonate and the like, disulfone compounds, diazoketosulfones, diazodisulfone compounds, and the like. 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, VNR Pillai, Synthesis,
(1), 1 (1980), A. Abad et al., Tetrahedron Lett.,
(47) 4555 (1971), DHR Barton et al., J. Chem.
Soc., (C), 329 (1970), U.S. Pat. No. 3,779,778, EP 126,712, and the like, can also be used compounds that generate an acid by light.

Among the above-mentioned photoacid generators (C), particularly effective ones are shown in the following <C-1> to <C-4.
>. <C-1>: An oxazole derivative represented by the following general formula (PAG1) or an S-triazine derivative represented by the following general formula (PAG2) substituted by a trihalomethyl group.

[0072]

Embedded image

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

[0074]

Embedded image

<C-2>: The following general formula (PAG3)
Or an iodonium salt represented by the general formula (PAG4)
A sulfonium salt represented by the formula:

[0076]

Embedded image

In the formula, Ar ¹ and Ar ² each independently represent a substituted or unsubstituted aryl group. R ²⁰³ , R ²⁰⁴ , R
²⁰⁵ independently represents a substituted or unsubstituted alkyl group or aryl group. Z ⁻ represents a counter anion, for example, BF ₄ ⁻ , AsF ₆ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ , Si
_{^{F 6 2-, ClO 4 -,}} CF 3 SO 3 - or the like of the perfluoroalkane sulfonate anion, an alkyl sulfonate anions such as camphorsulfonic acid anion, pentafluorobenzenesulfonic acid anion, benzenesulfonic acid anion, triisopropyl benzenesulfonic Aromatic sulfonic acid anions such as acid anions, condensed polynuclear aromatic sulfonic acid anions such as naphthalene-1-sulfonic acid anions, anthraquinone sulfonic acid anions, sulfonic acid group-containing dyes, and the like, but are not limited thereto. Not something. 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.

[0078]

Embedded image

[0079]

Embedded image

[0080]

Embedded image

[0081]

Embedded image

[0082]

Embedded image

[0083]

Embedded image

[0084]

Embedded image

The above onium salts represented by the general formulas (PAG3) and (PAG4) are known.
czyk et al., J. Am. Chem. Soc., 91, 145 (1969), A.
L. Maycok et al., J. Org.Chem., 35, 2532, (197
0), E. Goethas et al., Bull. Soc. Chem. Belg., 73,
546, (1964), HM Leicester, J. Ame. Chem. Soc., 5
1, 3587 (1929), JV Crivello et al., J. Polym. C
hem. Ed., 18, 2677 (1980), U.S. Pat. Nos. 2,807,648 and 4,247,473, and JP-A-53-101,331.

<C-3>: Disulfone derivative represented by the following general formula (PAG5) or iminosulfonate derivative represented by the following general formula (PAG6).

[0087]

Embedded image

Where 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.

[0089]

Embedded image

[0090]

Embedded image

[0091]

Embedded image

<C-4>: A diazodisulfone derivative represented by the following general formula (PAG7).

[0093]

Embedded image

In the formula, 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.

[0095]

Embedded image

In the present invention, the amount of the photoacid generator (C) to be added is usually in the range of 0.001 to 40% by weight, preferably 0 to 40% by weight, based on the solid content in the second resist composition. 0.01 to 20% by weight, more preferably 0.1%
It is used in the range of 10 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 second resist composition of the present invention preferably further contains an organic basic compound (D) as an acid scavenger. Organic basic compound (D) used in the present invention
Is preferably a compound which is more basic than phenol. In particular, nitrogen-containing basic compounds having the following structures (I) to (V) are preferably used. The use of this nitrogen-containing basic compound has an effect that a change in performance over time from exposure to post-heating can be reduced.

[0098]

Embedded image

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.

[0100]

Embedded image

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

More preferred compounds are nitrogen-containing cyclic compounds or two nitrogen atoms having different chemical environments in one molecule.
It is a basic nitrogen-containing compound having at least one compound. The nitrogen-containing cyclic compound more preferably has a polycyclic structure.
Preferred specific examples of the nitrogen-containing polycyclic compound include a compound represented by the following general formula (VI).

[0103]

Embedded image

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.

[0105]

Embedded image

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 basic nitrogen-containing 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 specific 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 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 amino Morpholine, substituted or unsubstituted aminoalkylmorpholine and the like. 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,
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 basic nitrogen-containing compound (D) used in the present invention can be used alone or in combination of two or more. The amount of the basic nitrogen-containing compound to be used is generally 0.001 to 10 parts by weight, preferably 0.01 to 5 parts by weight, based on the solid content of the photosensitive composition. 0.00
If it is less than 1 part by weight, the effect of adding the nitrogen-containing basic compound cannot be obtained. On the other hand, if it exceeds 10 parts by weight, sensitivity tends to decrease and developability of the unexposed portion tends to deteriorate.

Next, the solvent of the component (d) will be described. Preferred solvents used in the second resist composition of the present invention include, for example, ethylene glycol monoethyl ether acetate, cyclohexanone, 2-heptanone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, propylene Glycol monoethyl ether acetate, 3
-Methyl 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 the solvent is important because it affects the solubility in the second resist 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 second resist 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 second resist composition is preferably dissolved in the 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 second resist composition of the present invention is prepared as a solution with the solvent of the component (d) for the purpose of removing foreign substances and the like, and is then usually filtered, for example, with a filter having a diameter of about 0.05 to 0.2 μm. Preferably, it is used by filtration.

The second resist composition of the present invention may further contain, if necessary, a surfactant, an acid-decomposable dissolution inhibiting compound, a dye, a plasticizer, a photosensitizer, a crosslinking agent, a photobase generator, It may contain a base generator, a spectral sensitizer, a compound which promotes solubility in a developing solution, a compound whose basicity decreases upon exposure (photobase), and the like.

As the surfactant (E) which can be used in the second resist composition of the present invention, a fluorine-based and / or silicon-based surfactant is suitably used, and a fluorine-based surfactant, a silicon-based surfactant and Any surfactant containing both fluorine atoms and silicon atoms, or two or more surfactants can be contained. As these surfactants, for example, JP-A Nos. 62-36663, 61-226746, 61-226745, 61-226745, and
Nos. 62-170950, 63-34540, JP-A-7-230165, 8-6
The surfactants described in Nos. 2834, 9-54432 and 9-5988 can be mentioned, and 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 Chemical Co., Ltd.)
), Florado FC430, 431 (manufactured by Sumitomo 3M Limited),
Megafac F171, F173, F176, F189, R08 (Dai Nippon Ink Co., Ltd.), Surflon S-382, SC101, 102, 10
3, 104, 105, 106 (manufactured by Asahi Glass Co., Ltd.), Troysol S-36
6 (manufactured by Troy Chemical Co., Ltd.) or a silicon-based surfactant. In addition, polysiloxane polymer KP-341 (Shin-Etsu Chemical Co., Ltd.)
Can also be used as a silicon-based surfactant.

The amount of these surfactants to be added is usually 0.1% based on the solid content in the second resist composition of the present invention.
001% by weight to 2% by weight, preferably 0.01% by weight to
1% by weight. These surfactants may be added alone or in some combination. Examples of the surfactant that can be used in addition to the above include, specifically, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether. , Polyoxyethylene alkyl allyl ethers such as polyoxyethylene octyl phenol ether, polyoxyethylene nonyl phenol ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan Sorbitan fatty acid esters such as monooleate, sorbitan trioleate, sorbitan tristearate, polyoxyethylene sorbitan Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as laurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate And the like. The amount of these other surfactants is usually 2 parts by weight or less, preferably 1 part by weight or less, per 100 parts by weight of the solids in the second resist composition of the present invention.

Examples of the acid-decomposable dissolution inhibiting compound which can be used in the second resist composition of the present invention include, for example, those described in
Low-molecular acid-decomposable dissolution inhibiting compounds described in JP-A-134415 and JP-A-6-51519 can be used.

Examples of the plasticizer which can be used in the second resist composition of the present invention include JP-A-4-212960 and JP-A-8-208.
-262720, EP 735422, EP 416873, EP 439371, U.S. Pat.
No. 846690, specifically di (2-ethylhexyl) adipate, n-hexyl benzoate, di-n-octyl phthalate, di-n-butyl phthalate, benzyl-n-butyl phthalate, dihydro Aviethyl phthalate and the like can be mentioned.

Examples of the compound which can be used in the present invention and which promotes the solubility in a developer include, for example, JP-A No. 4-13 / 1990.
No. 4345, JP-A-4-217251, JP-A-7-1
No. 81680, JP-A-8-212597, 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. Also, salicylic acid, diphenolic acid,
Organic acids such as phenolphthalein can also be used, and JP-A Nos. 5-181263 and 7-92.
680, sulfonamide compounds described in JP-A-4-24
No. 8554, No. 5-181279, No. 7-92679
And carboxylic acid anhydrides described in JP-A No.
An alkali-soluble resin such as a polyhydroxystyrene resin described in 1-153869 can also be added.

Suitable dyes which 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 second resist composition of the present invention includes JP-A-7-28247 and EP 616258.
No. 5,525,443, JP-A-9-12770
0, EP 762207, U.S. Pat.
The ammonium salts described in No. 4, specifically, tetramethylammonium hydroxide, tetra-n-butylammonium hydroxide, betaine and the like can also be added, and JP-A-5-232706, JP-A-6-11835, JP-A-6-11835, and 2
No. 42606, No. 6-266100, No. 7-3338
No. 51, 7-333844, U.S. Pat.
No. 5, a compound (photobase) whose basicity decreases by exposure described in EP 677788 can also be added.

Further, the second resist composition of the present invention is added by adding a spectral sensitizer as described below to sensitize the photoacid generator to be used in a longer wavelength region than far ultraviolet where the photoacid generator does not have absorption. Can be made sensitive to i-line or g-line.
Examples of suitable spectral sensitizers include benzophenone, p, p'-tetramethyldiaminobenzophenone,
p, p'-tetraethylethylaminobenzophenone,
2-chlorothioxanthone, anthrone, 9-ethoxyanthracene, anthracene, pyrene, perylene, phenothiazine, benzyl, acridine orange, benzoflavin, setoflavin-T, 9,10-diphenylanthracene, 9-fluorenone, acetophenone, phenanthrene, 2-nitro Fluorene, 5-nitroacenaphthene, benzoquinone, 2-chloro-4-nitroaniline, N-acetyl-p-nitroaniline, p-nitroaniline, N-acetyl-4-nitro-1-naphthylamine, picramide, anthraquinone, -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 second resist composition of the present invention include JP-A-4-151156, JP-A-4-162040, JP-A-5-197148, and JP-A-5-197148.
No. 995, No. 6-194834, No. 8-146608
And 10-83079, EP 622682, and specifically, 2-nitrobenzyl carbamate, 2,5-dinitrobenzyl cyclohexyl carbamate, N-cyclohexyl-4-methylphenylsulfonamide , 1,1-dimethyl-2-phenylethyl-N-isopropylcarbamate 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
No. 158242, No. 5-158239, U.S. Pat.
No. 76143.

The second resist composition used in the present invention is previously coated on a substrate (eg, silicon / silicon dioxide coating), glass, ceramics, metal, or the like used in the manufacture of precision integrated circuit devices. It is used as a two-layer resist applied on the first resist provided. The layer formation of the photosensitive composition of the present invention comprises components (B) and (C),
Further, if necessary, compounds such as components (D) and (E) are dissolved in a solvent, and the resulting solution is applied by spin coating, spraying, or the like.

Examples of the developer for the second resist layer used in the present invention include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, and the like.
Primary amines such as n-propylamine, secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, and tetraamines Quaternary such as methylammonium hydroxide and tetraethylammonium hydroxide
Aqueous solutions of alkalis such as quaternary ammonium salts, cyclic amines such as pyrrole and piperidine can be used.
Further, an appropriate amount of an alcohol, a surfactant, an aromatic hydroxyl group-containing compound, or the like can be added to the aqueous solution of the above-mentioned alkalis. Among them, it is particularly preferable to use tetramethylammonium hydroxide.

The positive resist laminate of the present invention forms the first resist layer of the present invention on a substrate. The formation of this layer is performed by dissolving the compound contained in the first resist layer in an appropriate solvent, and applying the resulting solution by a spin coat method, a spray method, or the like. The thickness of the first resist layer is preferably from 0.1 to 2.0 μm, more preferably from 0.2 to 1.5 μm, and particularly preferably from 0.25 to 1.2 μm. If the thickness is less than 0.1 μm, it is not preferable from the viewpoint of antireflection and dry etching resistance. If the thickness is more than 2.0 μm, the aspect ratio becomes too high, and there is a problem that the formed fine pattern is easily collapsed, which is also unfavorable. .

Next, a second resist layer is formed.
Before that, it is preferable to heat-treat the first resist layer. The temperature of the heat treatment is preferably 150 to 250 ° C, more preferably 170 to 240 ° C, and 180 to 2 ° C.
30 ° C. is particularly preferred. When the temperature is lower than 150 ° C., when the second resist layer is applied, intermixing with the first resist layer is apt to occur, and when the temperature is higher than 250 ° C., the polymer in the first resist is easily decomposed and deteriorated. Absent. This heat treatment can be performed using a device such as a hot plate or a hot oven.
The time of the heat treatment varies depending on the heat treatment temperature, but in the case of the heat treatment at 180 to 230 ° C., 10 seconds to 10 seconds.
It is preferably set in the range of 00 seconds, more preferably 2 seconds.
0 to 600 seconds is preferred. If the time is shorter than 10 seconds, thermal curing is insufficient and intermixing with the second resist layer is apt to occur. If the time is longer than 1000 seconds, the number of substrates to be processed decreases, which is not preferable.

Next, a second resist layer is formed on the first resist layer, which can be performed in the same manner as the formation of the first resist layer. The thickness of the second resist layer is set to 0.1.
It is preferably from 0.3 to 0.6 μm, more preferably from 0.04 to 0.5 μm, particularly preferably from 0.04 to 0.5 μm.
5 to 0.45 μm. If the thickness is less than 0.03 μm, the pattern transferability to the first resist layer is poor, or a pinhole of the coating film is generated. If the thickness is more than 0.6 μm, the lithography performance is inferior.

The resulting two-layer resist is then subjected to a pattern forming step. As a first step, a pattern forming process is first performed on the second layer of the resist composition film. The mask is adjusted as required, and high-energy rays are irradiated through the mask, so that the resist composition in the irradiated portion is made soluble in an aqueous alkaline solution, and developed with an aqueous alkaline solution to form a pattern. Next, dry etching is performed as a second step. This operation is performed by oxygen plasma etching using the pattern of the film of the resist composition as a mask to form a fine pattern having a high aspect ratio. The etching of the organic polymer film by the oxygen plasma etching is exactly the same technique as the plasma etching used when the resist film is peeled off after the etching of the substrate is completed by the conventional photoetching operation. This operation can be performed by, for example, a cylindrical plasma etching apparatus using oxygen as a reactive gas, that is, an etching gas.
A gas such as a sulfurous acid gas may be mixed with oxygen gas.

The positive type silicone-containing resist laminate of the present invention can be used in the following steps. For example, on a semiconductor wafer, or on a substrate of glass, ceramics, metal, or the like, or on an antireflection layer or an organic film provided thereon, a spin coating method or a roller coating method is used.
It is applied to a thickness of ３3 μm. Then, heat and dry,
A circuit pattern or the like is printed by exposure to actinic rays or the like through an exposure mask and developed to obtain a positive image. Further, the substrate can be processed in a pattern by etching using the positive image as a mask. Typical application fields include a semiconductor manufacturing process such as an IC, a circuit board manufacturing such as a liquid crystal and a thermal head, and other photofabrication processes.

[0132]

[Examples] Hereinafter, Synthesis Examples, Examples and Comparative Examples are shown, but the present invention is not limited to the following Examples.

Synthesis Example 1 (Synthesis of P-2) Monomer Synthesis 10.6 g of methacrylic acid chloride, 15 g of 1-adamantanol, and 0.5 g of methoxyhydroquinone were dissolved in 70 ml of acetone.
3 g were added dropwise. After reacting at 60 ° C. for 4 hours, 0.5 liter of distilled water was added and collected by decantation. The product was purified by silica gel chromatography. The yield was 85%.

Polymer Synthesis After dissolving 13.3 g of the above monomer and 6.0 g of p-hydroxystyrene in 100 g of DMF, the reaction solution was added to 65 mL of the reaction solution.
° C, and at the same time, nitrogen was flowed into the reaction solution for 30 minutes. 35 mg of V-65 (product of Wako Pure Chemical Industries, Ltd.) as a polymerization initiator
Was added three times every two hours. The reaction product was recovered as a powder by reprecipitation in 1 liter of distilled water. GPC analysis of the obtained polymer showed that the weight average molecular weight was 11,500 in terms of standard polystyrene.

Synthesis Example 2 (Synthesis of P-4) Polymer Synthesis After dissolving 13.3 g of isobornyl methacrylate and 4.8 g of p-hydroxystyrene in 100 g of DMF,
The reaction solution was heated to 65 ° C., and nitrogen was added to the reaction solution at the same time
Diverted. 50 mg of V-65 (a product of Wako Pure Chemical Industries, Ltd.) was added three times every two hours as a polymerization initiator. The reaction product was recovered as a powder by reprecipitation in 1 liter of distilled water. When GPC analysis of the obtained polymer was performed,
The weight average molecular weight is 12600 in terms of standard polystyrene.
Met.

Synthesis Example 3 (Synthesis of B-3) Synthesis of Monomer 32.8 g of norbornene dicarboxylic anhydride was dissolved in 148 g of t-butanol, and 22.4 g of potassium t-butoxide was added thereto, followed by stirring at 80 ° C. for 3 hours. did. The reaction solution was returned to room temperature, and then diluted with diluted hydrochloric acid (5%) to 10 ° C.
After addition of 200 ml, 300 ml of ethyl acetate were added. After liquid separation, the ethyl acetate layer was washed twice with distilled water, and then ethyl acetate was distilled off under reduced pressure to obtain 41 g of mono-t-butyl norbornenedicarboxylate.

Synthesis of polymer 23.8 g of the above monoester was added to 200 ml of N, N-dimethylacetamide, and then ethyl chloroformate was added.
Then, while maintaining the reaction solution at 0 ° C., 11.0 g of triethylamine was added dropwise. After 18.0 g of 3-aminopropyltrimethoxysilane was added dropwise thereto over 1 hour, the reaction solution was gradually returned to room temperature and reacted for 5 hours. There cyclohexyltrimethylsilane 2
After adding 0.4 g, 10.0 g of distilled water, and 2.0 g of DBU, the mixture was heated to 80 ° C. and reacted for 12 hours while removing by-product methanol. After the temperature of the reaction solution was returned to room temperature, 100 ml of acetone was added thereto, and distilled water was gradually added thereto to precipitate a polymer component. After dissolving the precipitated polymer in acetone again, distilled water was added again to precipitate a polymer component and reduce a low molecular component in the polymer. The obtained polymer was dried under reduced pressure to obtain 25.9 g of a light brown target substance (a low-molecular component having a weight average molecular weight of 5,600 and a molecular weight of 1,000 or less was 9%).

Example 1 (1) Formation of First Resist Layer The above polymer (P-2) {component (A-1)} 5.0 g,
Hexamethylolmelamine {Component (A-2)} 0.35
g and di (t-amyl) phenyliodonium-2,
4,6-triisopropylsulfonate {component (A-
3) $ 0.125 g of methoxypropyl acetate 2
The solution was dissolved in 8.0 g, and the obtained solution was finely filtered through a membrane filter having a diameter of 0.1 μm to obtain a first resist composition. This composition was applied on a 6-inch silicon wafer using a spin coater Mark 8 manufactured by Tokyo Electron, and baked at 90 ° C. for 90 seconds to obtain a uniform film having a thickness of 0.55 μm. This was further heated at 200 ° C. for 90 seconds to obtain a lower resist layer having a thickness of 0.40 μm.

(2) Formation of Second Resist Layer The polymer (B-3) {component (B)} 0.9 g, the following compound (C-4) {component (C)} 0.05 g, and the following 0.005 g of the nitrogen-containing basic compound (D-1) 1,5-diazabicyclo [4.3.0] -5-nonene and 0.001 g of the following surfactant (W-1) were added to 9 g of methoxypropyl acetate. After dissolving, the resulting solution was dissolved in 0.
The solution was finely filtered through a 1 μm-diameter membrane filter to obtain a second resist composition. A second resist layer was similarly applied on the first resist layer and heated at 110 ° C. for 90 seconds to obtain a 0.20 μm-thick second resist layer.

[0140] The wafer thus obtained was used as an ArSI manufactured by ISI.
A resolving power mask was loaded on the F excimer stepper 9300, and exposure was performed while changing the exposure amount. Then, after heating in a clean room at 115 ° C. for 90 seconds, tetrahydroammonium hydroxide developing solution (2.38%) was used for 6 hours.
The pattern was developed for 0 second, rinsed with distilled water and dried to obtain a pattern (upper layer pattern). Further, a parallel plate type reactive ion etching apparatus DES-245 manufactured by Plasma System
Using R, the wafer having the upper layer pattern was etched (dry developed) to form a pattern in the lower layer. Etching gas is oxygen, pressure is 20 mTorr, applied power 1
00 mW / cm ² . The formed resist pattern was observed with a scanning electron microscope.

The following methods were used to evaluate the resolving power, line pattern undulation, and development residue. (1) Resolution: When the exposure amount was obtained when a 0.15 μm line / space of the mask was reproduced, the evaluation was made at the minimum dimension at which the line / space was separated and resolved in the lower layer. (2) Line pattern undulation: 0.15μ of the above mask
The deviation of the line from the straight line in the m line length direction of 20 μm was evaluated by an average value measured at arbitrary 20 points. (3) Number of development defects: The sample after exposure and development on which the line / space pattern obtained by the above method was formed was subjected to KL
A2112 (manufactured by KLA Tencor Co., Ltd.) was used to measure the number of development defects (Threshold: 12, Pixel Size = 0.3
9).

The results of Example 1 show that the resolution is 0.130 μm.
m, the undulation of the line pattern was 0.007 μm, and the number of development defects was as good as 4.

Examples 2 to 30 In the first example, the components (A-1) and (A-
In place of (2) and (A-3), each component (A-
1), (A-2) and (A-3) were used in the same amounts as in Example 1,
Further, instead of the components (B) and (C) of the second resist layer, the components (B) and (C) shown in Table 1 were used in amounts corresponding to the same moles. The nitrogen-containing basic compounds and surfactants shown in Table 1 were used.

[0144]

[Table 1]

Here, the following (A-2) component, (A-3) component, nitrogen-containing basic compound and surfactant were used.

(A-2) Component (A2-1): Hexamethylolmelamine (A2-2): Hexamethylolurea

(A-3) Component (A3-1): di (t-amyl) phenyliodonium-2,4,6-triisopropylsulfonate (A3-2): di (t-amyl) phenyliodonium-pentafluoro Phenylsulfonate (A3-3): cyclohexyl-p-toluenesulfonate

(C) Component (C-1): triphenylsulfonium-trifluoromethanesulfonate (C-2): tri (t-butylphenyl) sulfonium-perfluorobutanesulfonate (C-3): triphenylsulfonium-p Paddecylphenyl sulfonate (C-4): triphenylsulfonium-2,4,6-
Triisopropylphenyl sulfonate

Nitrogen-containing basic compound (D-1): 1,5-
Diazabicyclo [4.3.0] -5-nonene nitrogen-containing basic compound (D-2): 1,8-diazabicyclo [5.4.0] -7-undecene nitrogen-containing basic compound (D-3): 2,4,5-triphenylimidazole

Fluorosurfactant (W-1): Megafac F176 (Dai Nippon Ink Co., Ltd.) Fluorine / silicone surfactant (W-2): Megafac R08 (Dainippon Ink Co., Ltd.) ) Silicone surfactant (W-3): Polysiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.)

Exposure, development, and etching were performed in the same manner as in Example 1, and the resolution, line pattern undulation, and the number of development defects were evaluated in the same manner as in Example 1. Table 2 shows the results.

Comparative Examples 1 to 3 FHi-028D was used in place of the first resist layer of Example 1.
(Fujifilm Aurin's i-line resist)
The high-temperature heating conditions were 200 ° C / 90 seconds, 200 ° C /
Exposure, development, and etching were performed in the same manner as in Example 1 except that the heating time was 10 minutes and 200 ° C./60 minutes.
It was set to 3. Further, in the same manner as in Example 1, the resolution, the undulation of the line pattern, and the number of development defects were evaluated. Table 2 also shows the results.

[0153]

[Table 2]

From the above results, in Comparative Examples 1 to 3 in which the i-line resist was used in place of the first resist of the present invention, the resolution, line pattern undulation, and the number of development defects were increased by processing at a high temperature for a long time. Is improved, but it is still insufficient compared with the present invention. In the laminate of the present invention, good results can be obtained in good resolution, line pattern undulation, and number of development defects without performing high-temperature treatment. In the embodiment using the laminate of the present invention, since high-temperature treatment is not required, the decomposition of the polymer of the first resist layer by heat is suppressed to a low level, and the generation of components that adversely affect the performance of the second resist layer is reduced. It is estimated that it can be kept low. Further, since high-temperature treatment is not required, the suitability for production is improved, the throughput is improved, and the contamination of the device due to decomposition is suppressed.

[0155]

The positive resist laminate of the present invention can cope with exposure in the far ultraviolet region and has a high resolution. Also,
A resist pattern with less line waviness and development defects in a fine pattern of 0.2 μm or less can be formed. Furthermore, high-temperature treatment can be performed in a short time, and the suitability for production is excellent. Therefore, the laminate of the present invention is very suitably used for mass production of semiconductor substrates having ultrafine circuits.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 33/04 C08L 33/04 83/04 83/04 G03F 7/004 501 G03F 7/004 501 504 504 7 / 075 511 7/075 511 7/095 7/095 H01L 21/027 H01L 21/30 502R (72) Inventor Kazura Mizutani 4000 Kawajiri, Yoshida-cho, Haibara-gun, Shizuoka Prefecture ) 2H025 AA02 AA03 AB16 AC04 AC06 AC07 AC08 AD03 BE00 BE07 BE10 BF01 BF02 BF11 BF13 BF30 BG00 CB43 CB45 CB47 CC04 CC17 CC20 DA13 FA17 FA41 4J002 BG031 BG071 CH052 CP03 CP031 CP032 EU0 EB0 EU EB0 EB006 EUEB EB006 FD146 FD207 FD312 FD318 4J100 AB03P AB03Q AB03R AB07P AB07Q AB07R AL08P AL08Q AL08R AM05P BA03P BA03Q BA03R BA29P BA3 0P BB01P BB01Q BC07P BC07Q BC09P BC12P BC26P BC43P BC43Q JA38

Claims (5)

[Claims] 1. A two-layer resist having a first resist layer on a substrate and a second resist layer on the first resist layer,
The resist layer contains (A-1) a polymer containing both a repeating unit represented by the following general formula (1) and a repeating unit represented by the following general formula (2). B) a polysiloxane or polysilsesquioxane having a group decomposable by an acid and having a property of increasing the solubility in an alkaline developer by the action of an acid;
And (C) a compound capable of generating an acid upon irradiation with actinic rays or radiation. Embedded image In the formula, Y ¹ represents a hydrogen atom, an alkyl group, a cyano group or a halogen atom, L ¹ represents a divalent linking group which may have a substituent, and J may have a substituent. Represents a good alicyclic hydrocarbon group. a1 represents 0 or 1. Y ² has the same meaning as Y ¹ , and L ² has the same meaning as L ¹ . K represents an aryl group which may have a substituent. a2 and a3 are each independently
Represents 0 or 1. (A-1) used for the first resist layer
The polymer of the component contains in its structure at least one group selected from a hydroxyl group, a primary amino group and a secondary amino group, and the first resist layer further comprises (A-2)
A crosslinking agent activated by an acid and capable of reacting with the polymer of the component (A-1) to form a crosslinked structure;
3. The positive resist laminate according to claim 1, further comprising a compound that generates an acid by heat. 3. A polysiloxane or polysilsesquioxy having (B) an acid-decomposable group contained in the second resist layer and having a property of increasing the solubility in an alkaline developer by the action of an acid. The positive resist laminate according to claim 1, wherein the sun has a structure represented by the following general formula (3) in a side chain. Embedded image In the formula, J ¹ represents an alkylene group which may have a substituent, J ² is an arylene group which may have a substituent,
Substituent has unprotected alicyclic group, or an even better bridged alicyclic group which may have a substituent group, J ³ represents a divalent linking group, J ⁴ is 2 G represents a tetravalent linking group, and G represents a group decomposed by the action of an acid. k, l, m, and n each independently represent 0 or 1. However, k, l, m, and n are not all 0 at the same time. p represents an integer of 1 to 3. 4. The positive resist laminate according to claim 1, wherein the second resist layer further contains (D) a nitrogen-containing basic compound. 5. The positive resist laminate according to claim 1, wherein the second resist layer further contains (E) a fluorine-based and / or silicon-based surfactant.