JP2001215727A - Resist laminated body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resist laminated body adaptable to exposure in the far ultraviolet region, excellent in adhesion between the 1st and 2nd layers, having high resolving power, capable of forming a resist pattern having superior dry etching resistance, processable at a high temperature in a short time and excellent also in suitability to production. SOLUTION: The resist laminated body has a layer containing a resin having specified repeating structural units, a compound which generates an acid when heated and an acid-crosslinking compound which crosslinks the resin under the acid on a substrate and a silicon-containing radiation sensitive resist layer containing a silicon-containing resin and a compound which generates an acid when irradiated with active light or radiation on the above layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a resist laminate having a silicone-containing photosensitive composition for exposure to radiation such as ultraviolet rays, far ultraviolet rays, X-rays, electron beams, molecular beams, gamma rays, and synchrotron radiation. For more details, see I
The present invention relates to a resist laminate for microfabrication, which is used, for example, when manufacturing a circuit board or the like in a semiconductor manufacturing process such as C and has excellent adhesion to a substrate, high dry etching resistance, and excellent cost performance in device manufacturing. Typical application fields of the resist laminate of the present invention include semiconductor manufacturing processes such as ICs, manufacturing of circuit boards such as liquid crystals and thermal heads, and other photofabrication processes.

[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 -RIE
Silicon-containing polymers are usually used because they must be highly resistant. In particular, vinyl polymerization type polymers having a silicon atom in the side chain have been widely studied from the viewpoint of heat resistance and ease of synthesis. For example, JP-A-2-29
No. 3850, No. 10-282678, U.S. Pat.
Nos. 6071 and the like. The first resist layer imparts adhesion and film forming properties to the substrate, high dry etching resistance, immiscibility with the second resist layer (prevention of intermixing), high light absorption characteristics at the exposure wavelength, and the like. For this purpose, a method of solidifying a novolak resin or the like by high-temperature treatment is common and widely used. However, in the first resist layer containing the novolak resin, it is necessary to perform high-temperature treatment for a long time,
In the production of semiconductor devices and the like, there is also a problem that the suitability for production is extremely low. If the high-temperature treatment is performed in a short time, the solidification of the first resist layer becomes insufficient, causing a phenomenon (intermix) of mixing with the second resist layer, resulting in a problem of forming a pattern with a large amount of development residue and a second problem. There is also a problem that adhesion to the resist layer is poor. Further, there is room for improvement in dry etching resistance.

[0004]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a semiconductor device having an excellent adhesion between the first layer and the second layer, which can cope with exposure in the far ultraviolet region,
An object of the present invention is to provide a resist laminate having high resolution. Another object of the present invention is to provide a resist laminate that provides a resist pattern having excellent dry etching resistance. Another object of the present invention is to provide a resist laminate having high manufacturing suitability.

[0005]

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 layer containing, on a substrate, a resin having a repeating structural unit represented by the following general formula (I), a compound that generates an acid by heating, and an acid crosslinkable compound that crosslinks the resin with an acid; A resist laminate comprising a silicon-containing radiation-sensitive resist layer containing a silicon atom-containing resin and a compound that generates an acid upon irradiation with actinic rays or radiation.

[0006]

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In the formula (I), R represents a hydrogen atom, a hydroxyl group, a carboxyl group, a halogen atom, an alkyl group, an aryl group, an aralkyl group, a cycloalkyl group, an alkoxy group,
Represents an aralkyloxy group, an acyloxy group, an alkoxycarbonyl group, an aryloxy group, an aryloxycarbonyl group, or an arylcarbonyloxy group, and a plurality of Rs may be the same or different; Further, a plurality of substituents R may be bonded to each other to form a ring. m represents 1 or 2.

(2) The resin according to (1), wherein the resin having a repeating structural unit represented by the general formula (I) further contains a repeating structural unit represented by the following general formula (II). The resist laminate according to the above.

[0009]

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In the formula (II), R ₂ represents a hydrogen atom, an alkyl group, a halogen atom or a cyano group. R ₃ represents an aliphatic cyclic hydrocarbon group. (3) The resin (1) or (2), wherein the resin having a repeating structural unit represented by the general formula (I) further contains a repeating structural unit represented by the following general formula (III). 3. The resist laminate according to item 1.

[0011]

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In the formula (III), R ₂ has the same meaning as described above. R
₄ represents a divalent or higher valent hydrocarbon group. n represents an integer of 1 or more.

[0013]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be described below, but the present invention is not limited to these embodiments. The positive resist laminate of the present invention comprises a substrate, a first layer on the surface thereof (a resin having a repeating structural unit represented by the general formula (I), a compound capable of generating an acid by heating, and an acid). A silicon layer containing a resin containing a silicon atom and a compound generating an acid by irradiation with actinic rays or radiation; and a second layer (containing a resin containing a silicon atom) on the first layer. Radiation-sensitive resist layer). In order to achieve the object of the present invention more highly,
In the resin contained in the layer, the content of the repeating unit represented by the general formula (I) is at least 30 mol%, preferably at least 35 mol%, more preferably at least 40 mol% in all the repeating units. If it is less than 30 mol%, the dry etching resistance tends to be insufficient, which is not preferable.

In the general formula (I), examples of the halogen atom for R include a chlorine atom, a fluorine atom, an iodine atom and a bromine atom. As the alkyl group, a methyl group, an ethyl group, a propyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, a pentyl group, a hexyl group, a heptyl group, which may have a substituent, Examples thereof include those having 1 to 25 carbon atoms such as an octyl group, a t-amyl group, a decanyl group, a dodecanyl group, and a hexadecanyl group. The cycloalkyl group may have a substituent and has 3 to 25 carbon atoms such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, a cyclododecanyl group, and a cyclohexadecanyl group. Things. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group,
Those having 1 to 25 carbon atoms such as c-butoxy group or t-butoxy group, pentyloxy group, t-amyloxy group, n-hexyloxy group, n-octyloxy group, n-dodecaneoxy group and the like can be mentioned. .

Examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, an n-butoxycarbonyl group, an isobutoxycarbonyl group and a sec-butoxycarbonyl which may have a substituent. A group having 2 to 25 carbon atoms such as a t-butoxycarbonyl group, a pentyloxycarbonyl group, a t-amyloxycarbonyl group, an n-hexyloxycarbonyl group, an n-octyloxycarbonyl group, an n-dodecaneoxycarbonyl group, etc. One. As the acyloxy group, an acetoxy group, an ethylyloxy group, a butyryloxy group, a t-butyryloxy group, a t-amylyloxy group, an n-hexanecarbonyloxy group, an n-octanecarbonyloxy group, n -Dodecane carbonyloxy group, n
2 carbon atoms such as hexadecanecarbonyloxy group, etc.
To 25.

Examples of the aryl group include those having 6 to 20 carbon atoms which may have a substituent, and preferably include a phenyl group, a naphthyl group and an anthracenyl group. Examples of the aralkyl group include those having 7 to 20 carbon atoms such as a phenylmethyl group, a phenylethyl group, a naphthylmethyl group, and a naphthylethyl group. Examples of the aralkyloxy group include those having 7 to 20 carbon atoms such as a phenylmethyloxy group, a phenylethyloxy group, a naphthylmethyloxy group, and a naphthylethyloxy group which may have a substituent. Examples of the aryloxy group include those having 6 to 20 carbon atoms which may have a substituent,
Preferably, a phenyloxy group, a naphthyloxy group, an anthracenyloxy group and the like are mentioned.

Examples of the aryloxycarbonyl group include those having 7 to 21 carbon atoms which may have a substituent, preferably a phenyloxycarbonyl group, a naphthyloxycarbonyl group, an anthracenyloxycarbonyl group and the like. Is mentioned. Examples of the arylcarbonyloxy group include those having 7 to 21 carbon atoms which may have a substituent, and preferably include a phenylcarbonyloxy group, a naphthylcarbonyloxy group, and an anthracenylcarbonyloxy group. Can be

A plurality of substituents R may combine with each other to form a ring, and the ring may contain a hetero atom (for example, an oxygen atom, a nitrogen atom, a sulfur atom, etc.). , A 5- to 7-membered ring. Specifically, examples of the formed ring include a cyclopentane ring, a cyclohexane ring, a dioxolane ring, a furan ring, and a pyran ring. These rings may further have a substituent.

The above substituents or substituents on the ring are preferably an alkoxy group having 1 to 4 carbon atoms, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an acyl group, an acyloxy group, a cyano group. Group, hydroxyl group,
Examples include a carboxy group, an alkoxycarbonyl group, and a nitro group.

In the present invention, preferred substituents for R in the general formula (I) include a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a t-butyl group, a fluorine atom, a chlorine atom, a bromine atom, Trifluoromethyl group,
Hydroxyl, methoxy, ethoxy, propoxy, t-
Butoxy group, trifluoromethoxy group, phenyl group, phenoxy group, benzyl group, benzyloxy group, carboxy group, acetoxy group, methoxycarbonyl group, phenoxycarbonyl group, benzyloxycarbonyl group, phenylcarbonyloxy group, furan ring, pyran ring , A dioxolane ring.

Specific examples of the repeating structural unit represented by the general formula (I) are shown below, but the present invention is not limited thereto.

[0022]

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[0023]

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[0024]

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In the present invention, the resin contained in the first layer preferably contains a repeating structural unit represented by the general formula (II) in addition to the repeating unit represented by the general formula (I). Thereby, the profile and resolution of the resist layer as the second layer are improved. In order to achieve the object of the present invention to a higher degree, the content of the repeating unit represented by the general formula (II) in the resin contained in the first layer is usually based on the amount of the repeating unit (I). (Molar ratio:
(I) / (II)) 5/1 to 1/2, and 4/1 to 5 /
8 is preferable, and 10/3 to 5/6 is more preferable. When the content is less than the above range, the effect of adding the general formula (II) cannot be obtained, and when the content is more than the above range, dry etching resistance tends to deteriorate, which is not preferable.

The alkyl group represented by R ₂ in the general formula (II) includes an alkyl group having 1 to 3 carbon atoms, and the halogen atom includes a chlorine atom, a bromine atom and an iodine atom. R ₂ is more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and particularly preferably a hydrogen atom or a methyl group. As the aliphatic cyclic hydrocarbon group represented by R _{3 in} the general formula (II), the aliphatic cyclic hydrocarbon skeleton may be monocyclic or polycyclic. Specific examples include groups having a monocyclo, bicyclo, tricyclo, tetracyclo structure or the like having 5 or more carbon atoms. Its carbon number is 6
To 30 carbon atoms are preferred, and particularly preferably 7 to 25 carbon atoms. These alicyclic hydrocarbon groups may have a substituent. Hereinafter, structural examples of the alicyclic portion of the group containing the alicyclic hydrocarbon structure will be described.

[0027]

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[0028]

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[0029]

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In the present invention, preferred examples of the alicyclic moiety include an adamantyl group, a noradamantyl group, a decalin residue, a tricyclodecanyl group, a tetracyclododecanyl group, a norbornyl group, a cedrol group, and a cyclohexyl group. , Cycloheptyl group, cyclooctyl group,
Cyclodecanyl group, cyclododecanyl group, boronyl group,
An isobornyl group can be mentioned. More preferably, an adamantyl group, a decalin residue, a norbornyl group,
Cedrol group, cyclohexyl group, cycloheptyl group,
A cyclooctyl group, a cyclodecanyl group, a cyclododecanyl group, a boronyl group, an isobornyl group, a tricyclodecanyl group, and a tetracyclododecanyl group.

Examples of the substituent of these alicyclic hydrocarbon groups include an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group, an alkoxy group, a carboxyl group and an alkoxycarbonyl group. As the alkyl group, a lower alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group is preferable, and a methyl group, an ethyl group, a propyl group, and an isopropyl group are more preferable. Examples of the substituent of the substituted alkyl group include a hydroxyl group, a halogen atom and an alkoxy group. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group. Hereinafter, specific examples of the repeating structural unit represented by Formula (II) will be shown, but the present invention is not limited thereto.

[0032]

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[0033]

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[0034]

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In the present invention, the resin contained in the first layer includes a repeating unit represented by the general formula (III) in addition to the repeating unit represented by the general formula (I) and the repeating structural unit represented by the general formula (II). It preferably contains a structural unit. Thereby, the thermosetting property of the first layer is improved, and the intermixing with the second layer, which is the upper layer, can be further suppressed. In the resin contained in the first layer, the content of the repeating unit represented by the general formula (III) is usually 1 to 30 mol%, preferably 3 to 25 mol%, based on all repeating units.
More preferably, it is 5 to 20 mol%. If the content is less than the above range, the effect of adding the general formula (III) cannot be obtained, and if the content is more than the above range, dry etching resistance tends to deteriorate, which is not preferable.

R ₄ in the general formula (III) is a hydrocarbon group having a valence of 2 or more [(n + 1) or more], preferably 2 or more and 6 or less, more preferably 2 or more and 4 or less. . As the hydrocarbon group, a divalent alkylene group having 2 to 18, preferably 2 to 10, more preferably 2 to 6 carbon atoms, or one or more hydrogen atoms in the alkylene group is removed to form a trivalent or higher valent group. Resulting from the above-mentioned general formula (I
A hydrocarbon group (which may have a substituent) in which one or more hydrogen atoms in the aliphatic cyclic hydrocarbon group represented by R _{3 of} I) have been removed to form a divalent or higher valent group, or And a divalent or higher valent group formed by combining the above group and an oxygen atom.

[0037]

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[0038]

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In the present invention, the above resin is a copolymer containing, besides each of the above repeating units, another repeating unit for the purpose of improving film-forming properties, adhesion, developability and the like. Is also good. As a monomer corresponding to such another repeating unit, other than the above repeating units, for example, acrylates, methacrylates,
Compounds having one addition-polymerizable unsaturated bond selected from acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, and the like can be given.

Specifically, for example, acrylic esters such as alkyl (the alkyl group has 1 to 1 carbon atoms)
Acrylates (e.g., methyl acrylate, ethyl acrylate, propyl acrylate, amyl acrylate, ethylhexyl acrylate, octyl acrylate, tert-octyl acrylate, chloroethyl acrylate, benzyl acrylate, Methoxybenzyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, etc.);

Methacrylic esters, for example, alkyl (the alkyl group preferably has 1 to 10 carbon atoms) methacrylate (for example, methyl methacrylate,
Ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, amyl methacrylate, hexyl methacrylate, benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, etc.);

Acrylamides, for example, acrylamide, N-alkylacrylamide (alkyl group having 1 to 10 carbon atoms, for example, methyl group, ethyl group, propyl group, butyl group, t-butyl group, heptyl group, octyl group , 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 (alkyl having 1 to 10 carbon atoms, for example, methyl, ethyl, t-butyl, ethylhexyl, hydroxyethyl, cyclohexyl) Groups, etc.), N, N-dialkyl methacrylamide (alkyl groups include ethyl group, propyl group, butyl group, 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 resin used in the present invention is not particularly limited, but it is compatible with the components of the first layer, such as a thermal crosslinking agent and a thermal acid generator, an organic solvent, and a film-forming property. From 1,000 to 1,000,000 is preferable, and more preferably 2000 to 1,000,000.
It is preferably from 100,000 to 100,000. Specific examples of the resin used in the present invention include the following, but are not limited thereto.

[0049]

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[0050]

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[0051]

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[0052]

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In the present invention, the content of the resin in the first layer is usually 5 to 40% by weight, preferably 7 to 35% by weight, based on the total solid content in the first layer. More preferably, it is 10 to 30% by weight.

The first layer comprises a compound which generates an acid by heat (also referred to as a "thermal acid generator") and an acid activated,
And an acid-crosslinkable compound (also referred to as an “acid-crosslinking agent”) capable of forming a crosslinked structure by reacting with a resin containing a repeating unit represented by the above general formula (I). As the acid cross-linking agent, known ones can be widely used, and examples thereof include an acid cross-linking agent which can react with the resin under acidic conditions to form a bond. For example, a melamine compound substituted with at least one group selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group,
A benzoguanamine compound, a glycoluril compound or a urea compound, or a polyvalent methylol compound of a phenol compound or a methyl ether compound thereof is preferred. Examples of the alkoxymethyl group include methoxymethyl, ethoxymethyl, propoxymethyl, butoxymethyl and the like. As an acyloxymethyl group,
Acetyloxymethyl and the like can be mentioned. The number of methylol groups, alkoxymethyl groups, and acyloxymethyl groups contained in these compounds per molecule is 2 to 6, preferably 5 to 6, in the case of melamine, and in the case of glycoluril compounds and benzoguanamine compounds. Is 2 to 4, preferably 3 to 4. 3 for urea compounds
~ 4.

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 alkoxymethyl group-containing compound can be obtained by heating the methylol group-containing compound in an alcohol in the presence of an acid catalyst such as hydrochloric acid, sulfuric acid, nitric acid, and methanesulfonic acid. 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. Examples of the polyhydric methylol compound of a phenol compound or its methyl ether compound include a hexamethylol form of Trisp-Pa (structure shown below) or its methyl ether form.

[0056]

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In the present invention, among these, hexamethoxymethylmelamine, tetramethoxymethylbenzoguanamine,
Tetramethoxymethyl glycoluril compounds, polyhydric methylol compounds of phenol compounds or methyl ether compounds thereof are preferable, and polyhydric methylol compounds of phenol compounds or methyl ether compounds thereof are more preferable. In the present invention, the content of the acid crosslinking agent in the first layer is 2 to 50% by weight in terms of solid content,
Preferably it is 5 to 30% by weight.

The thermal acid generator is a compound which generates an acid by heating (heat treatment). In the present invention, the acid crosslinker is activated by the acid to crosslink the resin. The temperature at which the acid begins to be generated is 150-220
C., more preferably 170 to 200 C.,
Specifically, 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, a sulfonate compound or a diaryliodonium salt can be used, and preferably, a sulfonate compound or It is a diaryliodonium salt. The sulfonic acid ester compound is preferably an alkyl ester of an organic sulfonic acid having 3 to 20 carbon atoms, specifically, 2-propanol, 2-butanol,
-Sulfonates of secondary alcohols such as pentanol and cyclohexanol are preferred. Examples of the diaryliodonium salt compound include salts of a diaryliodonium cation and an organic sulfonic acid anion, SbF ₆ anion, PF ₆ anion or AsF ₆ anion. Here, the anion of an organic sulfonic acid is preferable as the anion. Here, examples of the aryl group in the cation portion include a phenyl group, a naphthyl group, an anthryl group, and a phenanthryl group which may have a substituent. Specific examples of the diaryliodonium salt compound include the following compounds.

[0059]

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[0060]

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[0061]

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[0062]

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Among these, salts of diaryliodonium and organic sulfonic acid are preferred from the viewpoint 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 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. Examples of the group are the same as those described above.) Or an arylsulfonate which may have a halogen atom as a substituent is preferable 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 above-mentioned thermal acid generator is usually added at a ratio of 0.5 to 10 parts by weight, preferably 1 to 5 parts by weight, based on 100 parts by weight (solid content) of the resist composition of the first layer. .

The first layer used in the present invention may further include, in addition to the resin, the acid crosslinking agent, and the thermal acid generator described above, other materials for improving film forming properties, heat resistance, dry etching resistance, and the like. May be added. 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, JP-A-50-125
As described in JP-A-806, a condensate of phenol or cresol substituted with an alkyl group having 3 to 8 carbon atoms and formaldehyde, together with the phenol resin as described above, such as a t-butylphenol aldehyde resin May be used in combination. Further, a polymer having a phenolic hydroxy group-containing monomer such as N- (4-hydroxyphenyl) methacrylamide as a copolymer component can also be used.

In the first layer of the present invention, if necessary, JP-A-4-122938 and JP-A-2-27595 may be used.
An aromatic polyhydroxy compound described in JP-A Nos. 5 and 4-230754 may be added. The first layer in the invention may contain an organic basic compound.

As a solvent for dissolving each component in the composition of the first layer in the present invention, methyl ethyl ketone,
Ketones such as cyclohexanone, alcohol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether, ethers such as dioxane and ethylene glycol dimethyl ether, cellosolve esters such as methyl cellosolve acetate and ethyl cellosolve acetate, butyl acetate, and methyl lactate Fatty acid esters such as ethyl lactate, halogenated hydrocarbons such as 1,1,2-trichloroethylene, dimethylacetamide, N-methylpyrrolidone, dimethylformamide,
A highly polar solvent such as dimethyl sulfoxide can be exemplified. These solvents can be used alone or as a mixture of a plurality of solvents.

In the first layer of the present invention, a dye, a plasticizer, an adhesion aid, a surfactant and the like can be blended if necessary. Specific examples thereof include dyes such as methyl violet, crystal violet, and malachite green, stearic acid, acetal resins, phenoxy resins, alkyd resins, plasticizers such as epoxy resins, and adhesion of hexamethyldisilazane, chloromethylsilane, and the like. There are auxiliary agents and surfactants such as nonylphenoxypoly (ethyleneoxy) ethanol and octylphenoxypoly (ethyleneoxy) ethanol. In particular, in the case of a dye, a dye containing an alkali-soluble group such as an aromatic hydroxyl group or a carboxylic acid group in the molecule, such as glutamine, is particularly preferably used.

Next, the silicon-containing radiation-sensitive resist layer as the second layer will be described. The second layer contains a silicon-containing resin and a photoacid generator. The second layer has radiation sensitivity, and may be a negative type chemically amplified resist layer or a positive type chemically amplified resist layer. In the case of a positive-type chemically amplified resist layer, the silicon-containing resin contained therein may be an acid-decomposable resin having a property of increasing the dissolution rate in an alkali developing solution by the action of an acid, or may have alkali solubility. An alkali-soluble silicon-containing resin may be used. However, in the case of an alkali-soluble silicon-containing resin, the second layer further contains a low molecular weight dissolution inhibiting compound having an acid-decomposable group. In the case of a negative type chemically amplified resist layer, the layer contains a crosslinkable compound which is crosslinked by an acid, and the silicon-containing resin contained therein is an alkali-soluble silicon-containing resin having alkali solubility and also has a crosslinkable group. In the present invention, the second layer is preferably a positive chemically amplified resist layer, and the silicon-containing resin is preferably an acid-decomposable resin.

As the positive type chemically amplified resist layer as the second layer, for example, SPIE Vol. 3678 21
4 (1999), 562, SPIE Vol.
3678 241 (1999), SPIE Vo
l. 3678 420 pages (1999), SPIE V
ol. 3333 621 (1998), 484
Page, SPIE Vol. 3333 122 (1998)
And Japanese Patent Publication No. 7-99435, Japanese Patent Publication No. 3-44290, Japanese Patent Application Laid-Open No. 5-249683, Japanese Patent Application Laid-Open No. 7-140667, Japanese Patent Application Laid-Open No. 6-35199, and Japanese Patent Application Laid-Open No. 6-35199. 7-219231, JP-A-8-231
2305023, JP-A-10-324748, JP-A-1
And Japanese Patent Application Laid-Open No. 8-334901.

In the present invention, an acid-decomposable resin containing a Si element (hereinafter also referred to as a high molecular silicone compound) includes a group decomposed by the action of an acid (also referred to as an acid-decomposable group) and a Si element (a silicon compound). Atoms). Where Si
The element may be included as a Si element-containing substituent on the side chain in the high molecular silicone compound, or may be included in the resin skeleton. In the present invention, the Si element contains Si as a side chain.
It is preferable to be included as an element-containing substituent. Examples of such a Si element-containing substituent include a substituent having a silyl group (—Si (R) ₃ ) which may have a substituent. The polymer silicone compound is preferably a resin having a substituent represented by — (CH ₂ ) n —Si (R ₁ ) (R ₂ ) (R ₃ ) on the side chain of the polymer.
Here, R ^{1 to} R ³ each independently represent an alkyl group, a haloalkyl group, a halogen atom, an alkoxy group, a trialkylsilyl group, or a trialkylsilyloxy group.
n represents 0 or 1. R ^{1 to} R ³ each independently represent a group selected from an alkyl group, a haloalkyl group, a halogen atom, an alkoxy group, a trialkylsilyl group, and a trialkylsilyloxy group. The alkyl group is preferably a straight-chain or branched alkyl group having 1 to 10 carbon atoms, more preferably a straight-chain or branched alkyl group having 1 to 6 carbon atoms, still more preferably a methyl group, an ethyl group,
n-propyl group, i-propyl group, n-butyl group, i-
A butyl group, an s-butyl group, and a t-butyl group. Haloalkyl groups include chloromethyl, bromomethyl,
An iodomethyl group is mentioned.

The alkoxy group is a linear or branched alkoxy group having 1 to 6 carbon atoms, more preferably a methoxy group, an ethoxy group, an n-propyloxy group, an i-propyloxy group, an n-butoxy group, i-butoxy group, s
-Butoxy group and t-butoxy group, particularly preferred are methoxy and ethoxy groups.

The alkyl group of the trialkylsilyl is a linear or branched alkyl group having 1 to 6 carbon atoms, more preferably a methyl group, an ethyl group, an n-propyl group, or an i-alkyl group.
-Propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, and most preferred is a methyl group. The alkyl group of the trialkylsilyloxy group is a linear or branched alkyl group having 1 to 6 carbon atoms, more preferably a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, i-butyl group, s
-Butyl group and t-butyl group, and among them, the most preferred is a methyl group. n represents 0 or 1, and is preferably 1. Thereby, the roughness (irregularity) of the edge of the line is improved.

The high molecular silicone compound contains a repeating unit represented by the following general formula (Ia) and a repeating unit represented by at least one of the following general formulas (IIa) and (IIb). It is preferable to use a resin whose solubility in an alkali developing solution is increased by the action of an acid.

Formula (Ia)

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In the formula (Ia), R ^{1 to} R ³ and n are as defined above.

Formula (IIa)

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In the formula (IIa), Y is a hydrogen atom, a methyl group,
Represents a group selected from a cyano group and a chlorine atom. L represents a single bond or a divalent linking group. Q represents a hydrogen atom or a group capable of decomposing with an acid to generate a carboxylic acid.

Formula (IIb)

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In the formula (IIb), X ¹ and X ² each independently represent a group selected from an oxygen atom, a sulfur atom, —NH— and —NHSO ₂ —. L ¹ and L ² each independently represent a single bond or a divalent linking group. A ¹ is -Q or -C
OOQ is represented, and when X ¹ is an oxygen atom and L ¹ represents a single bond, A ¹ represents -Q. A ² is a hydrogen atom, a cyano group,
Hydroxyl group, -COOH, -COOR ', -CO-NH-
R '', an optionally substituted alkyl group, an optionally substituted cyclic hydrocarbon group, an alkoxy group, -Q or -C
OOQ (here, R ′ and R ″ each independently represent an alkyl group which may have a substituent). Q represents a group capable of decomposing with an acid to generate a carboxylic acid.

In the present invention, the resin preferably further contains a repeating unit represented by the following general formula (III).

General formula (III)

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In the formula (III), Z represents an oxygen atom or N—R ³ . R ³ represents a hydrogen atom, a hydroxyl group, a linear or branched alkyl group, or —O—SO ₂ —R ⁴ . R ⁴ represents an alkyl group or a trihalomethyl group.

In the repeating unit (IIa), Y represents a group selected from a hydrogen atom, a methyl group, a cyano group and a chlorine atom. L represents a single bond or a divalent linking group. Q represents a hydrogen atom or a group capable of decomposing with an acid to generate a carboxylic acid. The group capable of decomposing with an acid to generate a carboxylic acid is a group which is decomposed / eliminated from a resin by an acid generated from a photoacid generator upon exposure to generate a —COOH group. Specific examples of such groups include t
Tertiary alkyl groups such as -butyl group and t-amyl group, isobornyl group, 1-ethoxyethyl group, 1-butoxyethyl group, 1-alkoxyethyl group such as 1-isobutoxyethyl group and 1-cyclohexyloxyethyl group , 1-methoxymethyl group, 1-ethoxymethyl group and other alkoxymethyl groups, tetrahydropyranyl group, tetrahydrofurfuryl group, trialkylsilyl group, 3-oxocyclohexyl group, 2-methyl-adamantyl group, mevalonic lactone And a 2- (γ-butyrolactonyloxycarbonyl) -2-propyl group.

The following are specific examples of the repeating unit represented by the above general formula (Ia), but the present invention is not limited to these specific examples.

[0085]

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In the repeating unit (IIb), X ¹ and X ² each independently represent an oxygen atom, a sulfur atom, -NH-, -N
Represents a group selected from HSO ₂ —. L ¹ and L ² each independently represent a single bond or a divalent linking group.

The divalent linking group in L ¹ and L ² is specifically an alkylene group, a substituted alkylene group, an ether group, a thioether group, a carbonyl group, an ester group,
A single group selected from the group consisting of an amide group, a sulfonamide group, a urethane group, and a urea group, or a combination of two or more groups may be used. Examples of the alkylene group and substituted alkylene group in L ¹ and L ² include groups represented by the following formulas. -[C (Ra) (Rb)] r- wherein Ra and Rb represent a hydrogen atom, an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group, or an alkoxy group;
Both may be the same or different. As the alkyl group, a lower alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group is preferable, and a methyl group, an ethyl group, a propyl group, and an isopropyl group are more preferable. As the substituent of the substituted alkyl group,
Examples include a hydroxyl group, a halogen atom and an alkoxy group. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group. Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom. r represents an integer of 1 to 10.

A ² represents a hydrogen atom, a cyano group, a hydroxyl group, -C
OOH, -COOR ', -CO-NH-R ", an optionally substituted alkyl group, an alkoxy group, -Q or -C
OOQ. (R ′ and R ″ each independently represent an alkyl group which may have a substituent.) A ² , R ′,
In R '', the alkyl group includes 1 to 10 carbon atoms.
Is preferably a straight-chain or branched alkyl group having 1 to 6 carbon atoms, more preferably a methyl group, an ethyl group, an n-propyl group, an i-propyl group, and n -Butyl group, i-butyl group, s
-Butyl group and t-butyl group. Similarly, the alkoxy group is a linear or branched alkoxy group having 1 to 6 carbon atoms, more preferably a methoxy group, an ethoxy group,
-Propyloxy group, i-propyloxy group, n-butoxy group, i-butoxy group, s-butoxy group, t-butoxy group, and particularly preferred are methoxy and ethoxy groups. Similarly, Q is the same group as Q in the repeating unit (IIa). Examples of the further substituent of the above alkyl group and alkoxy group include halogen atoms such as fluorine, chlorine, bromine and iodine, and alkoxy groups such as methoxy, ethoxy, propoxy and butoxy. As the cyclic hydrocarbon group for A ² , a cyclopropyl group, a cyclopentyl group,
Cyclohexyl group, adamantyl group, 2-methyl-2-
An adamantyl group, a norbornyl group, a boronyl group, an isobornyl group, a tricyclodecanyl group, a dicyclopentenyl group, a nobornane epoxy group, a menthyl group, an isomenthyl group, a neomenthyl group, a tetracyclododecanyl group, and the like can be given. The bond forming the ring of these cyclic hydrocarbon groups may have an ester bond or a carbonyl bond. Further substituents of the cyclic hydrocarbon group include a hydroxyl group, a halogen atom, a carboxyl group, an alkoxy group, an acyl group, a cyano group, an acyloxy group and the like. Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom. As the alkoxy group, a methoxy group, an ethoxy group,
Examples thereof include those having 1 to 4 carbon atoms such as a propoxy group and a butoxy group. Examples of the acyl group include a formyl group and an acetyl group. Examples of the acyloxy group include an acetoxy group.

The following are specific examples of the repeating unit represented by the above general formula (IIa), but the present invention is not limited to these specific examples.

[0090]

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[0091]

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Specific examples of the repeating unit represented by the general formula (IIb) include the following, but the present invention is not limited to these specific examples.

[0093]

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[0094]

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[0095]

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[0096]

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[0097]

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In the repeating unit (III), Z represents an oxygen atom, NR ³ . R ³ represents a hydrogen atom, a hydroxyl group, a linear or branched alkyl group, or —O—SO ₂ —R ⁴
Represents R ⁴ represents an alkyl group or a trihalomethyl group.
The alkyl group of R ³ and R ⁴ is preferably a straight-chain or branched alkyl group having 1 to 10 carbon atoms, more preferably a straight-chain or branched alkyl group having 1 to 6 carbon atoms, and further preferably methyl Group, ethyl group, n-propyl group, i-
Propyl group, n-butyl group, i-butyl group, s-butyl group and t-butyl group. Specific examples of the repeating unit represented by the general formula (III) include the following, but the present invention is not limited to these specific examples.

[0099]

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[0100]

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The above-mentioned silicon-containing resin according to the present invention is further copolymerized with the following monomers so as to provide a repeating unit constituting the resin within a range where the effects of the present invention can be effectively obtained. However, the present invention is not limited to the following monomers. Thereby, the performance required for the resin, particularly (1) solubility in a coating solvent, (2) film forming property (glass transition point), (3) alkali developability, and (4) film loss (hydrophobicity, alkali (Selection of a soluble group), (5) adhesion of the unexposed portion to the substrate, (6) dry etching resistance,
Can be finely adjusted. Examples of such a copolymerizable monomer include, for example, an acrylate, a methacrylate, an acrylamide, a methacrylamide, an allyl compound, a vinyl ether, and an addition-polymerizable unsaturated bond selected from vinyl esters. Compounds having one can be mentioned.

Specifically, for example, acrylates 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, 2-hydroxyethyl acrylate 2,2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, benzyl acrylate, methoxybenzyl acrylate, furfuryl acrylate, Tetrahydrofurfuryl acrylate, etc.);

Methacrylic esters such as alkyl (preferably having 1 to 10 carbon atoms in the alkyl group) methacrylate (eg, methyl methacrylate,
Ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate,
Benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate,
5-hydroxypentyl methacrylate, 2,2-dimethyl-3-hydroxypropyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, etc.);

Acrylamides, for example, acrylamide, N-alkylacrylamide, (alkyl having 1 to 10 carbon atoms, for example, methyl, ethyl, propyl, butyl, t-butyl, heptyl, octyl Group, 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 group, etc.), N-
Hydroxyethyl-N-methylacrylamide, N-2
-Acetamidoethyl-N-acetylacrylamide and the like;

Methacrylamides, for example, methacrylamide, N-alkyl methacrylamide (alkyl having 1 to 10 carbon atoms, for example, methyl, ethyl, t-butyl, ethylhexyl, hydroxyethyl, cyclohexyl) Groups, etc.), N, N-dialkylmethacrylamide (an alkyl group includes an ethyl group, a propyl group, a butyl group, etc.), N-hydroxyethyl-N-methylmethacrylamide 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), 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.); acrylic acid, methacrylic acid, crotonic acid, itaconic acid, acrylonitrile, methacrylonitrile and the like.

In the silicon-containing resin of the present invention, a repeating unit represented by the general formula (Ia), at least one of the repeating units (IIa) and (IIb), and a component which is preferable to be copolymerized. General formula (II
The content of the repeating unit represented by I) is determined as follows: oxygen plasma etching resistance of the desired resist, sensitivity, pattern cracking prevention, substrate adhesion, resist profile,
Further, it can be appropriately set in consideration of the resolving power, heat resistance, and the like, which are necessary requirements of general resists. Generally, in the resin for the second layer of the present invention, the resin represented by the general formula (Ia)
The content of the repeating unit represented by the formula is 10 to 90 mol%, preferably 15 to 7 mol%, based on all repeating units.
0 mol%, and more preferably 20 to 50 mol%.
Further, the content of at least one of the repeating units (IIa) and (IIb) is 5 to all the repeating units.
It is 50 mol%, preferably 10 to 40 mol%. The content of the repeating unit (III) is usually 10 to 90 mol%, preferably 15 to 90 mol%, based on all repeating units.
７０70 mol%, more preferably 20-60 mol%.

In the above resin, monomers corresponding to the repeating units represented by the general formula (Ia), and the monomers represented by the general formulas (IIa) and (II)
b) is obtained by copolymerizing a monomer corresponding to at least one of the repeating units, and a monomer corresponding to the repeating unit represented by the general formula (III) if necessary in the presence of a polymerization catalyst. . Alternatively, the compound of general formula (I)
The monomer corresponding to the repeating unit represented by the general formula (II
After further copolymerizing maleic anhydride with the monomer corresponding to the repeating unit of a), or copolymerizing maleic anhydride with the monomer corresponding to the repeating unit represented by the general formula (Ia), There is also a method in which a repeating unit derived from maleic anhydride of the obtained copolymer is partially subjected to ring-opening esterification with an alcohol or hydrolysis under basic or acidic conditions to synthesize.

The weight average molecular weight of the resin for the second layer according to the present invention is preferably from 1,000 to 200,000 in terms of polystyrene by the GPC method. When the weight average molecular weight is less than 1,000, heat resistance and dry etching resistance are deteriorated, so that it is not preferable.
If the molecular weight exceeds 000, the developing property is deteriorated, and the viscosity becomes extremely high, so that the film forming property is deteriorated.

In the photoresist composition for the second layer in the present invention, the compounding amount of the silicon-containing resin according to the present invention in the whole composition is 40 to 9 in the total resist solid content.
9.99% by weight is preferable, and more preferably 50 to 9% by weight.
9.97% by weight.

The compound (photoacid generator) used in the second layer of the present invention, which is decomposed by irradiation with actinic rays or radiation to generate an acid, is a photoinitiator for cationic photopolymerization or a photoinitiator for photoradical polymerization. An agent, a photo-decoloring agent for pigments, a photo-discoloring agent, or a compound capable of generating an acid by a known light used in a micro resist or the like, and a mixture thereof can be appropriately selected and used. For example, onium salts such as diazonium salts, ammonium salts, phosphonium salts, iodonium salts, sulfonium salts, selenonium salts, and arsonium salts, organic halogen compounds, organic metal / organic halogen compounds, and photoacid generators having an O-nitrobenzyl-type protecting group And disulfone compounds which generate sulfonic acid upon photolysis typified by an agent, iminosulfonate 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, compounds capable of generating an acid by light described in U.S. Pat. No. 3,779,778 and European Patent No. 126,712 can also be used.

Among these, diazodisulfone compounds, iodonium or sulfonium salts are preferable, and iodonium salts or sulfonium salts are more preferable, from the viewpoints of acid generation efficiency by exposure, appropriate diffusion of acid, and stability in resist. . The iodonium salt is preferably an iodonium salt represented by the following general formula (PAG3), and the sulfonium salt is preferably a sulfonium salt represented by the following general formula (PAG4).

[0116]

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In the formulas (PAG3) and (PAG4), 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,
Examples include an alkoxy group, a nitro group, a carboxyl group, an alkoxycarbonyl group, an acyl group, an acyloxy 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, it is an aryl group having 6 to 14 carbon atoms, an alkyl group having 1 to 8 carbon atoms, or a substituted derivative thereof. Preferred examples of these 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, an acyl group, an acyloxy group, a hydroxy group, a mercapto group and a halogen atom. Can be

[0119] Z- represents a counter anion, for example BF ₄ ^{-,
_{AsF 6 -, PF 6 -,}} SbF 6 -, SiF 6 2-, ClO 4 -,
CF ₃ SO ₃ ^- perfluoroalkane sulfonate anion such as, pentafluorobenzenesulfonic acid anion, sulfonic acid anion having aliphatic hydrocarbon group or an aromatic hydrocarbon group such as a naphthalene-1-sulfonic acid anion, anthraquinone sulfonic acid Examples of the dye include an anion and a sulfonic acid group-containing dye, but are not limited thereto.

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 of the photoacid generator include the following compounds, but are not limited thereto.

[0122]

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[0123]

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[0124]

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[0125]

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[0126]

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[0127]

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[0128]

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[0129]

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[0130]

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[0131]

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[0132]

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[0133]

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[0134]

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The onium salts represented by the general formulas (PAG3) and (PAG4) are described, for example, in JW Knapczyk et al., JA
m. Chem. Soc., 91, 145 (1969), ALMaycok et al., J. Org. C
hem., 35, 2532, (1970), E. Goethas et al., Bull. Soc. Ch.
em. Belg., 73, 546, (1964), HM Leicester, J. Ame.
Chem. Soc., 51, 3587 (1929), JVCrivello etal, JP
olym.Chem.Ed., 18,2677 (1980), U.S. Pat.No. 2,807,648
No. 4,247,473, JP-A-53-101,331 and the like.

In the present invention, the addition amount of the photoacid generator in the composition for the second layer is 0.01 to 0.01% based on the total solid content.
20% by weight is preferred, more preferably 0.05 to 15%.
%, More preferably 0.1 to 10% by weight.

The first and second layers in the present invention may contain an organic basic compound. 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).

[0138]

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Here, R ²⁵⁰ , R ²⁵¹ and R ²⁵² are the same or different and are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms,
An aminoalkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group 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 are bonded to each other to form a ring; It may be formed.

[0140]

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In the formula (E), R ²⁵³ , R ²⁵⁴ , R ²⁵⁵ and R ²⁵⁶ are the same or different and represent an alkyl group having 1 to 6 carbon atoms.

Further preferred compounds are nitrogen-containing 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 are 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 aminomorpholine, substituted or unsubstituted aminoalkylmorpholine, etc. Is mentioned. Preferred substituents are an amino group, aminoalkyl group, alkylamino group, aminoaryl group, arylamino group, alkyl group, alkoxy group, acyl group, acyloxy group, aryl group, aryloxy group, nitro group, hydroxyl group, cyano group It is. Particularly preferred compounds include guanidine, 1,1-dimethylguanidine, 1,1,3,3-tetramethylguanidine,
-Aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-dimethylaminopyridine, 4-dimethylaminopyridine, 2-diethylaminopyridine, 2- (aminomethyl) pyridine, 2-amino-3-methylpyridine, 2- Amino-4-methylpyridici, 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-virazoline,
Examples include, but are not limited to, N-aminomorpholine, N- (2-aminoethyl) morpholine, and the like.

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 to 10 parts by weight, preferably 0.01 to 5 parts by weight, per 100 parts by weight of the 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 resist composition for the second layer of the present invention may further contain, if necessary, a surfactant, a dye, a pigment, a plasticizer,
A compound having two or more phenolic OH groups for promoting the solubility in a photosensitizer and a developer can be contained.

Examples of the surfactant include a fluorine-based surfactant, a silicon-based surfactant, a surfactant containing both a fluorine atom and a silicon atom, and a nonionic surfactant. I do. Among them, a fluorine-based surfactant, a silicon-based surfactant, and a surfactant containing both a fluorine atom and a silicon atom are particularly preferable. As these surfactants, for example, JP-A-62-36663, JP-A-61-226746, JP-A-61-226745, JP-A-62-17095
No. 0, JP-A-63-34540, JP-A-7-230165, JP-A-8-6
No. 2,834, JP-A-9-54432, JP-A-9-5988, 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, (manufactured by Shin-Akita Kasei Co., Ltd.), Florado FC430, 431 (Sumitomo 3M Co., Ltd.)
), Megafac F171, F173, F176, F189, R08 (Dai Nippon Ink Co., Ltd.), Surflon S-382, SC101, 102,
Fluorinated surfactants such as 103, 104, 105, and 106 (manufactured by Asahi Glass Co., Ltd.) and silicon-based surfactants can be exemplified. Also, polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can be used as a silicon-based surfactant.

As other surfactants, specifically, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether and polyoxyethylene oleyl ether; Ethylene octyl phenol ether, polyoxyethylene alkyl allyl ethers such as polyoxyethylene nonyl phenol ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, Sorbitan trioleate, sorbitan fatty acid esters such as sorbitan tristearate, polyoxyethylene sorbitan monolaurate, Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate; Can be mentioned. The amount of the surfactant is usually 0.001% by weight to 2% by weight, preferably 0.1% by weight, based on the solid content in the composition of the present invention.
It is from 01% by weight to 1% by weight. These surfactants may be added alone or in some combination.

The photoresist layer, which is the second layer in the present invention, is formed by dissolving the above components in a solvent that dissolves the above components and coating the solution on the first layer. Examples of the solvent include propylene glycol monomethyl ether acetate, propylene glycol monoalkyl ether acetates such as propylene glycol monoethyl ether acetate, methyl lactate, alkyl lactates such as ethyl lactate, propylene glycol monomethyl ether, propylene glycol monoethyl ether and the like. Ethylene glycol monoalkyl ethers such as propylene glycol monoalkyl ethers, ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate; -Heptanone, γ-butyrolactone, methoxyp Selected from alkyl alkoxylates such as methyl pionate and ethyl ethoxypropionate, alkyl pyruvates such as methyl pyruvate and ethyl pyruvate, N-methylpyrrolidone, N, N-dimethylacetamide, dimethyl sulfoxide and the like. It is applied using at least one solvent.

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.

[0149] The resist laminate of the present invention is formed on the substrate by the first step.
A resist layer is formed. 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 set to 0.
It is preferably from 1 to 10 μm, more preferably from 0.2 to 2 μm, particularly preferably from 0.25 to 1.
5 μm. If the thickness is less than 0.1 μm, it is not preferable from the viewpoints of antireflection and dry etching resistance.
If the thickness is larger than m, the aspect ratio becomes too high, and there is a problem that the formed fine pattern is likely to collapse, which is also not preferable.

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 obtained two-layer resist is then subjected to a pattern forming step. As a first step, first, a pattern forming process is performed on the second layer of the resist composition film. The mask is adjusted as required, and the irradiated portion of the resist layer as the second layer is made soluble in an alkaline aqueous solution by irradiating a high-energy ray through this mask. To form here,
As high energy rays (exposure light), KrF, ArF,
Deep ultraviolet rays such as F ₂ , Kr ₂ , KrAr, and Ar ₂ , vacuum ultraviolet rays, X-rays, and electron beams can be used. The exposure light source is an ArF or F ₂ excimer laser. Next, dry etching is performed as a second step. In this operation, the first layer is etched by oxygen plasma etching using the pattern of the resist layer film 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.

[0153]

[Examples] Hereinafter, Synthesis Examples, Examples and Comparative Examples are shown, but the present invention is not limited to the following Examples. 1. Synthesis Example of Lower Layer Resin (1) Synthesis of Resin (1) Styrene (monomer corresponding to general formula [I]), isobornyl acrylate (monomer corresponding to general formula [II]),
Hydroxyethyl methacrylate (a monomer corresponding to the general formula [III]) was charged into a reaction vessel at a molar ratio of 50/45/5, and dissolved in tetrahydrofuran to prepare a solution having a solid content of 25%. This was heated at 60 ° C. under a nitrogen stream. When the reaction temperature was stabilized, 0.5 mol% of a radical initiator V-601 manufactured by Wako Pure Chemical Industries, Ltd. was added to start the reaction. Three
After heating for 0 hours, the reaction mixture was cooled to room temperature and poured into distilled water to precipitate a white powder. The precipitated powder was taken out by filtration, dried, and the above-mentioned resin (1) as the target product was obtained. When the molecular weight analysis of the obtained resin (1) by GPC was attempted, it was 31400 (weight average) in terms of polystyrene. Also, from the NMR spectrum, the resin (1)
Was styrene / isobornyl acrylate / hydroxyethyl methacrylate = 51/43/6.
In the same manner as in Synthesis Example (1), the following resin (2) to
(20) was synthesized.

[0154]

[Table 1]

[Synthesis of Resin for Second Layer] Synthesis Example (1) (Synthesis of Resin (1-1)) 11.4 g of trimethylallylsilane, 9.8 g of maleic anhydride, and 5.3 g of acrylonitrile were dried in THF34.
g, and then heated to 65 ° C. under a nitrogen stream. When the reaction temperature was stabilized, an initiator V-65 manufactured by Wako Pure Chemical Industries, Ltd. was added at 10 mol% of the total moles of the monomers to start the reaction. After reacting for 6 hours, the reaction mixture was diluted twice with THF, and then poured into a large amount of hexane to precipitate a white powder. Next, in order to reduce residual monomers and low molecular components, the precipitated powder was dissolved in acetone,
The polymer was precipitated by gradually adding hexane thereto. The precipitated polymer was washed with hexane / acetone (8/2) and dried, and then acetone 100m
and 10 g of t-butanol and 12.2 g of 4-dimethylaminopyridine were added thereto.
Reacted for hours. When the temperature of the reaction solution was lowered to 20 ° C., 15 g of methyl iodide was added, and the mixture was reacted at room temperature for 6 hours. After evaporating the solvent under reduced pressure and concentrating, the polymer was poured into 1 L of distilled water and reprecipitated. Then, drying was performed under reduced pressure to obtain a resin (1-1). As a result of GPC measurement, the molecular weight of the obtained resin (1-1) was 6600 in weight average using polystyrene as a standard sample, and the content of components having a molecular weight of 1000 or less was 4% by area ratio of GPC.

Resins (1-2) to (1) were prepared in the same manner as described above.
-4) was obtained. The molar ratio and the weight average molecular weight of each repeating unit of the resins (1-1) to (1-4) are shown below.

[0157]

Embedded image

Synthesis Example (5) (Synthesis of Resin (2-1)) 11.4 g of trimethylallylsilane, 9.8 g of maleic anhydride, and 6.4 g of t-butyl acrylate were dried in TH.
After adding to 34 g of F, the mixture was heated to 65 ° C. under a nitrogen stream.
When the reaction temperature becomes stable, initiator V manufactured by Wako Pure Chemical Industries, Ltd.
-65 was added in an amount of 10 mol% of the total number of moles of the monomers to start the reaction. After reacting for 6 hours, the reaction mixture is
After diluting twice with HF, throw it into a large amount of hexane,
A white powder was deposited. Next, in order to reduce residual monomers and low molecular components, the precipitated powder was dissolved in acetone, and hexane was added little by little to precipitate a polymer. The precipitated polymer was washed with hexane / acetone (8/2) and dried, and then acetone 100
and 10 g of t-butanol and 4-
12.2 g of dimethylaminopyridine was added and reacted at 80 ° C. for 6 hours. When the temperature of the reaction solution was lowered to 20 ° C., 15 g of methyl iodide was added, and the mixture was reacted at room temperature for 6 hours. After evaporating the solvent under reduced pressure and concentrating, the polymer was poured into 1 L of distilled water and reprecipitated. Then, drying was performed under reduced pressure to obtain a resin (2-1). As a result of GPC measurement, the molecular weight of the obtained resin (2-1) was 5600 in weight average using polystyrene as a standard sample, and the content of components having a molecular weight of 1000 or less was 4% by area ratio of GPC.

The resins (2-1) to (2) were prepared in the same manner as described above.
-7) was obtained. The molar ratio and the weight average molecular weight of each repeating unit of the resins (2-1) to (2-7) are shown below.

[0160]

Embedded image

[0161]

Embedded image

Example 1 (1) Formation of First Layer Resin component: Resin 1 5.0 g Acid crosslinking agent component: hexamethylolmelamine 0.35 g Thermal acid generator component: (described in Table 2) 0.125 g was converted to methoxy The solution was dissolved in 28 g of propyl acetate, and the resulting solution was finely filtered through a membrane filter having a diameter of 0.1 μm to obtain a resist composition for the first layer. This composition was applied to a silicon wafer by a coater CDS-65 manufactured by Canon.
And heated at 110 ° C. for 90 seconds to form a film having a thickness of 0.1 mm.
A uniform film of 62 μm was obtained. This is further added to 200 ° C, 90
After heating for 1 second, a first resist layer having a thickness of 0.48 μm was obtained.

(2) Formation of Second Resist Layer Silicon-containing resin component: Resin 1-1 0.9 g Photoacid generator component: (PAG4-6) 0.05 g Other components: 1,8-diazabicyclo [ 5.4.0] -7-undecene 0.006 g Surfactant (Troysol S-366; manufactured by Troy Chemical Co., Ltd.) 0.01 g was dissolved in propylene glycol monomethyl ether acetate (PGMEA) 9 g to obtain a solution. 0.1 μ
The resultant was finely filtered through a membrane filter having a diameter of m to obtain a resist composition for the second layer. On the above-mentioned first resist layer, the composition for the second resist layer is similarly applied, and 115
By heating at 90 ° C. for 90 seconds, a second resist layer having a thickness of 0.20 μm was obtained.

[0164] The wafer obtained in this manner was transferred to Ar I manufactured by ICI.
An excimer laser stepper 9300 was loaded with a resolving power mask and exposed while changing the exposure amount. afterwards,
After heating at 125 ° C. for 90 seconds in a clean room, a tetrahydroammonium hydroxide developer (2.38)
%), Rinsed with distilled water and dried to obtain a pattern (upper layer pattern). The pattern was observed with a scanning electron microscope. Further, the wafer having the upper layer pattern was etched (dry-developed) using a parallel plate reactive ion etching apparatus manufactured by ULVAC to form a pattern in the lower layer. The etching gas was oxygen, the pressure was 20 mTorr, the applied power was 100 mW / cm ² , and the etching time was 15 minutes. The formed resist pattern was observed with a scanning electron microscope.

The dry etching resistance, the adhesion between the first layer and the second layer, the resist pattern profile in the second layer, the resolution in the second layer, the second
The presence or absence of scum at the time of pattern formation in the layer and the presence or absence of intermixing between the first layer and the second layer were evaluated. (1) Dry etching resistance: Fujifilm Olin Co., Ltd. i-line photoresist FHi-630 and a coating film of 1.0μm thickness of the measurement sample was CF ₄ etching respectively, to measure the film thickness after etching. FHi-63
The relative ratio (film thickness variation of the measurement sample / film thickness variation of FHi-630) is 1.
未 満 for less than 2 and △ for 1.2 to 1.3
Those that exceeded were evaluated as ×. (2) Adhesion between the first layer and the second layer: the pattern of the second layer (0.2 μm in thickness) after alkali development was observed with an SEM,
At the exposure dose at which the isolated pattern of 0.18 μm was reproduced, the peeling of the isolated pattern having various line widths was evaluated. When the adhesion between the first layer and the second layer is good, a finer pattern remains. (3) Resist pattern profile in the second layer:
0.18 μm line and space pattern (1:
In the exposure amount reproduced in 1), the side wall angle with the surface of the first layer (lower layer) of the pattern (side wall angle of 85 to 90 degrees is good),
The top shape of the pattern (the one with a rectangular shape is good), the presence or absence of a skirting shape at the bottom of the pattern is 0.14 μm
(1: 1) (no good). Here, good ones are ○,
When there was a problem only in the top shape, Δ was given when there was a problem in two or more items. (4) Resolution in the second layer: The pattern of the second layer (0.2 μm thick) after alkali development was observed by SEM.
The critical resolving power at the exposure amount at which an 18 μm line / space (1: 1) pattern was reproduced was evaluated. (5) Presence or absence of scum at the time of pattern formation in the second layer: 0.14 μm line and space pattern (1: 1) at an exposure amount where a 0.18 μm line and space pattern (1: 1) is reproduced. The presence or absence of scum when forming was evaluated. When there was no scum, it was evaluated as ○, and when there was scum, it was evaluated as ×. (6) Presence or absence of intermixing of the first layer and the second layer: the first layer (lower layer) is formed as described above, and the film is immersed in a coating solvent (PGMEA) for the second layer (upper layer) for 5 minutes. The thickness was measured, and its variation rate, ((initial film thickness-film thickness after immersion) / initial film thickness) × 100, was evaluated. A smaller one is preferred.

The results of Example 1 show that, as shown in Table 3 below, the upper layer was cured very quickly, the adhesion between the first layer and the second layer was excellent, and the dry etching resistance was good. The resist pattern profile and resolution in the second layer were excellent, and scum was not generated during pattern formation in the second layer, and intermixing between the first and second layers was substantially eliminated.

Examples 2 to 25 The resin component of the first resist layer of Example 1, the acid crosslinking agent component,
Example 1 was replaced with the components shown in Tables 2 and 3 in the same amounts as in Example 1 in place of the thermal acid generator component, the silicon-containing resin component of the second resist layer, the photoacid generator component, and other components. Exposure, development and etching treatments were carried out in the same manner as described above, and the resultant was observed with a scanning electron microscope, and evaluated in the same manner as in Example 1. The results are shown in Tables 4 and 5.

[0168]

[Table 2]

[0169]

[Table 3]

In Tables 2 and 3, A-1 is a phenol resin (PR54046, manufactured by Sumitomo Durez). Comparative Example FHi-028D was used in place of the first resist layer of Example 1.
Exposure, development and etching were carried out in the same manner as in Example 1, except that D (resist for i-line manufactured by Fuji Film Ohlin Co., Ltd.) was used and the high-temperature heating condition was set to 200 ° C./90 seconds. Observation and evaluation were performed in the same manner as in Example 1. Table 5 shows the results.

[0171]

[Table 4]

[0172]

[Table 5]

From the evaluation results of Examples 1 to 25 and Comparative Example, the following is clear. That is, the resist laminate of the example is solidified by a high-temperature treatment for a short time of 90 seconds, and a resist pattern having excellent dry etching resistance and adhesion can be formed. On the other hand, in the case of the comparative example in which the conventional i-line resist is used for the first resist layer, the performance is inferior to that of the example in the same short-time high-temperature treatment as in the example, and the suitability for manufacturing is significantly reduced in the case of the long-term treatment. Further, by adopting a preferred embodiment of the present invention, the resolution and profile of the second layer are further excellent, and the occurrence of scum and the occurrence of intermixing between the first and second layers during pattern formation in the second layer are prevented. be able to.

[0174]

The positive resist laminate of the present invention can provide a resist laminate which can cope with exposure in the far ultraviolet region, has excellent adhesion between the first layer and the second layer, and has high resolution. Further, a resist pattern having excellent dry etching resistance can be formed. Further, 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 25/00 C08L 25/00 33/00 33/00 G03F 7/039 601 G03F 7/039 601 7/075 511 7/075 511 H01L 21/027 H01L 21/30 502R 573 F term (reference) 2H025 AA00 AA02 AA09 AA14 AB15 AB16 AB17 AC01 AC04 AC05 AC06 AC07 AC08 AD01 AD03 BE00 BG00 DA40 FA03 FA12 FA17 FA41 2H096 AA00A EA05 FA01 GA08 JA04 KA02 KA06 KA19 4J002 BC011 BC101 BG001 BG011 BG021 BG041 BG051 EE027 EJ016 ET016 EU186 EV217 EV247 EW007 EY007 EY027 FD146 FD157 FD207 GF00 GP03 4J100 AB00P AB02P AB04P AB07P AB08P AB09P AB10P AL08Q AL08R AL16Q AL16R AL26Q AL26R AQ25P BA02P BA02R BA03P BA03R BA04P BA05P BA06P BA08R BA16P BA16Q BA16R BA20P BB18P BC04P BC04Q BC07Q BC08Q BC09Q BC09 R BC12Q BC12R BC26Q BC43P CA05 JA38 5F046 LB01 NA01 NA14 PA08 PA09

Claims (3)

[Claims] 1. A layer containing, on a substrate, a resin having a repeating structural unit represented by the following general formula (I), a compound that generates an acid by heating, and an acid-crosslinkable compound that crosslinks the resin with the acid. And a silicon-containing radiation-sensitive resist layer containing a silicon-containing resin and a compound that generates an acid upon irradiation with actinic rays or radiation. Embedded image In the formula (I), R is a hydrogen atom, a hydroxyl group, a carboxyl group, a halogen atom, an alkyl group, an aryl group, an aralkyl group, a cycloalkyl group, an alkoxy group, an aralkyloxy group, an acyloxy group, an alkoxycarbonyl group, an aryloxy group, Represents an aryloxycarbonyl group or an arylcarbonyloxy group, and a plurality of Rs may be the same or different; Further, a plurality of substituents R may be bonded to each other to form a ring. m represents 1 or 2. 2. The resin according to claim 1, wherein the resin having a repeating structural unit represented by the general formula (I) further contains a repeating structural unit represented by the following general formula (II). Resist laminate. Embedded image In the formula (II), R ₂ represents a hydrogen atom, an alkyl group, a halogen atom or a cyano group. R ₃ represents an aliphatic cyclic hydrocarbon group. 3. The resin according to claim 1, wherein the resin having a repeating structural unit represented by the general formula (I) further contains a repeating structural unit represented by the following general formula (III). The resist laminate according to the above. Embedded image In the formula (III), R ₂ has the same meaning as described above. R ₄ represents a divalent or higher valent hydrocarbon group. n represents an integer of 1 or more.