JPH11102065A - Photosensitive resin composition, pattern forming method using the composition, and method for manufacturing electronic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain sufficient resolution, sensitivity and aspect ratio of the photosensitive resin composition by incorporating an acid-decomposable substance having a urea group or aminopyrazine group or a radiation-sensitive substance, which prevent the dissolution of a polymer having carboxyl groups in an alkaline developing solution. SOLUTION: The photosensitive resin composition contains the polymer having an alicyclic structure and carboxylic groups, a substance to be allowed to release an acid by radiation and a substance represented by formula I or/and a substance represented by formula II, and in formulae I and II, A1 is an atom of group VI of the periodic table; each of R1 and R2 is a 3-50C organic group and at least one of them is a hydroxyl group to be deprotected with an acid or/and a carboxyl group; A2 is an O, S, or N atom; and each of R3 and R4 is a 3-40C organic group and at least one of them is a hydroxyl group to be deprotected with an acid; or/and a carboxyl group. This makes the obtained pattern forming method superior in resolution performance and free from swelling.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] 1. Field of the Invention [0002] The present invention relates to a positive photoresist composition, a method of forming a pattern using the same, and a method of manufacturing an electronic device using the same.

The positive photoresist composition according to the present invention contains an acid-decomposable substance or a radiation-sensitive substance having a urea group or an aminopyrazine group, which inhibits dissolution of a polymer having a carboxyl group in an alkaline developer. Features. A polymer having a carboxyl group is useful as a photoresist material for an ArF excimer laser required for ultrafine processing.

[0003]

2. Description of the Related Art In photolithography, a submicron pattern is required to be formed in accordance with high integration of a semiconductor integrated circuit. Therefore, it is necessary to shorten the wavelength of the light source of the exposure apparatus.
Consideration of m) has begun.

A conventional resist (novolak resin, polyvinyl phenol) contains an aromatic ring and has low transparency with respect to the wavelength of an ArF laser. As a resist transparent to an ArF laser, a chemically amplified resist, t-butyl methacrylate copolymer (JP-B-2-27660)
No.) has been proposed. However, this resist lacks dry etch resistance. A polymethacrylic acid copolymer having an alicyclic hydrocarbon group in a side chain (Japanese Patent Publication No. 4-39665) has been proposed as a resist that is transparent to far ultraviolet rays and has dry etch resistance similar to that of an aromatic ring. ing.

[0005]

In a polymethacrylic acid copolymer having an alicyclic hydrocarbon group in the side chain, the proportion of the alicyclic hydrocarbon structure in the polymer is increased in order to improve dry etch resistance. In such a case, swelling and peeling occur during development, and sufficient resolution, sensitivity, and aspect ratio cannot be obtained.

Accordingly, an object of the present invention is to provide a positive photoresist composition which can solve the above-mentioned problems, and a pattern forming method using the same.

[0007]

According to the present invention, the following technical means are used to achieve the above object.

The first means is to provide a carboxyl polymer having an alicyclic hydrocarbon structure, a substance capable of generating an acid by radiation, and

[0009]

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Wherein A ₁ is a group VI atom of the periodic table, R
₁ or R ₂ is an organic group having 3 to 50 carbon atoms, at least one of which has a hydroxyl group deprotected by an acid and / or a carboxyl group), or / and ( 2)

[0011]

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Wherein A ₂ is an oxygen atom, a sulfur atom or a nitrogen atom, and R ₃ or R ₄ is a group having 3 to 4 carbon atoms, respectively.
A radiation-sensitive resin composition comprising a substance represented by formula (1) having at least one of a hydroxyl group and / or a carboxyl group which is deprotected by an acid.

A second means is to provide a carboxyl polymer having an alicyclic hydrocarbon structure,

[0014]

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(Wherein A ₃ is an atom of Group VI of the periodic table, R
₅ or R ₆ is an organic group having 3 to 50 carbon atoms, respectively.
And / or a radiation-sensitive substance represented by the formula

[0016]

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Wherein A ₄ is an oxygen atom, a sulfur atom or a nitrogen atom, and R ₇ or R ₈ is a carbon atom having 3 to 4 carbon atoms, respectively.
A radiation-sensitive resin composition comprising a radiation-sensitive substance represented by formula (1).

The third means is a carboxyl polymer having an alicyclic hydrocarbon structure and an organic group hydrolyzed by an alkali developing solution, a substance generating an acid by radiation,
(Formula 1)

[0019]

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(Wherein A ₁ is a group VI atom of the periodic table, R
₁ or R ₂ is an organic group having 3 to 50 carbon atoms, at least one of which has a hydroxyl group deprotected by an acid and / or a carboxyl group), or / and ( 2)

[0021]

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(Wherein A ₂ is an oxygen atom, a sulfur atom or a nitrogen atom, and R ₃ or R ₄ is a group having 3 to 4 carbon atoms, respectively)
A radiation-sensitive resin composition comprising a substance represented by formula (1) having at least one of a hydroxyl group and / or a carboxyl group which is deprotected by an acid.

The fourth means is a carboxyl polymer having an alicyclic hydrocarbon structure and an organic group hydrolyzed by an alkali developing solution;

[0024]

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(Where A ₃ is an atom of Group VI of the periodic table, R
₅ or R ₆ is an organic group having 3 to 50 carbon atoms, respectively.
And / or a radiation-sensitive substance represented by the formula

[0026]

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Wherein A ₄ is an oxygen atom, a sulfur atom or a nitrogen atom, and R ₇ or R ₈ is a carbon atom having 3 to 4 carbon atoms, respectively.
A radiation-sensitive resin composition comprising a radiation-sensitive substance represented by formula (1).

The fifth means is that (formula 1) is (formula 5)

[0029]

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Wherein A ₅ is an oxygen atom or a sulfur atom,
A ₆ and A ₇ are each an oxygen atom or a carbonyloxy group, P ₁ and P ₂ are each an acid-decomposable organic group, R ₉ or R ₁₀ is an alkyl group having 2 to 30 carbon atoms, an aryl group, An aralkyl group, a heterocyclic group, an alicyclic hydrocarbon group, a or b represents 1 to 5), and 1 to 100 parts by weight based on 100 parts by weight of the total resin. The radiation-sensitive resin composition according to claim 1.

The sixth means is that (Chem. 1) is (Chem. 6)

[0032]

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Wherein A ₈ is an oxygen atom or a sulfur atom,
A ₉ is an oxygen atom or a carbonyloxy group, P ₃ is an acid-decomposable organic group, R ₁₁ is an alkyl group having 2 to 30 carbon atoms, an aryl group, an aralkyl group, a heterocyclic group, an alicyclic hydrocarbon group,
R ₁₂ is an alkyl group having 2 to 30 carbon atoms, an aryl group, an aralkyl group, a heterocyclic group, an alicyclic hydrocarbon group, and c is 1 to 1
The radiation-sensitive resin composition according to claim 1, wherein 0 and d represent 1 to 5).

The seventh means is that (Chem. 2) is replaced by (Chem. 7)

[0035]

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(Where A ₁₀ or A ₁₁ is an oxygen atom or a carbonyloxy group, A ₁₂ is an oxygen atom, a sulfur atom or a nitrogen atom, A ₁₃ is a methylene group, P ₄ or P
₅ is an acid-decomposable organic group, and R ₁₃ has 2 to 30 carbon atoms.
Alkyl, aryl, aralkyl, heterocyclic,
The radiation-sensitive resin composition according to claim 1, wherein an alicyclic hydrocarbon group, e + g is 1 to 5, f is 1 to 5, and h is 0 to 5).

Eighth means is that (Chem. 3) is (Chem. 8)

[0038]

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(Where A ₁₄ is an oxygen atom or a sulfur atom,
A ₁₅ and A ₁₆ each represent an oxygen atom or an amino group,
Q ₁ and Q ₂ are each a radiation-sensitive organic group; R ₁₄ or R ₁₅ is an alkyl group having 2 to 30 carbon atoms, an aryl group, an aralkyl group, a heterocyclic group, an alicyclic hydrocarbon group, i or The radiation-sensitive resin composition according to claim 2, wherein the compound represented by the formula (1) contains 1 to 100 parts by weight based on 100 parts by weight of the total resin.

The ninth means is that (Chem. 3) is replaced by (Chem. 9)

[0041]

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Wherein A ₁₇ is an oxygen atom or a sulfur atom,
A ₁₈ is an oxygen atom or an amino group, Q ₃ is a radiation-sensitive organic group, R ₁₆ is an alkyl group having 2 to 30 carbon atoms, an aryl group,
Aralkyl group, heterocyclic group, alicyclic hydrocarbon group, R ₁₇ is an alkyl group having 2 to 30 carbon atoms, aryl group, aralkyl group, heterocyclic group, alicyclic hydrocarbon group, k is 1 to 10, l Represents 1 to 5), The radiation-sensitive resin composition according to claim 2 or 4, wherein

The tenth means is that (Chem. 4) is replaced by (Chem. 10)

[0044]

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Wherein A ₁₉ or A ₂₀ is an oxygen atom or an amino group, A ₂₁ is an oxygen atom, a sulfur atom or a nitrogen atom, A ₂₂ is a methylene group, and Q ₄ or Q ₅ is a radiation-sensitive organic compound. R ₁₈ represents an alkyl group having 2 to 30 carbon atoms, an aryl group, an aralkyl group, a heterocyclic group, an alicyclic hydrocarbon group, m + o represents 1 to 5, n represents 1 to 5, and p represents 0 to 5. 5) The radiation-sensitive resin composition according to claim 2, wherein

The eleventh means is a step of applying the radiation-sensitive resin composition according to any one of claims 1 to 10 on a substrate and drying.
A method for forming a pattern, comprising: irradiating an electromagnetic wave through a photomask, and developing the radiation-sensitive resin composition with an alkaline developer to form a pattern.

The twelfth means is a step of applying and drying the radiation-sensitive resin composition according to any one of claims 1 to 10 on a circuit forming surface or a protective film forming surface of an electronic circuit, and irradiating an electromagnetic wave through a photomask. And forming a pattern by developing the radiation-sensitive resin composition with an alkaline developer.

In the present invention, the acid-decomposable substance having a urea group or aminopyrazyl group or the radiation-sensitive substance is a polymer having a carboxyl group (carboxyl polymer).
Acts as a dissolution controlling agent. Heretofore, no compound exhibiting a high dissolution inhibiting effect on a carboxyl polymer has been known. Therefore, in a photoresist having a carboxyl polymer, swelling occurred in unexposed and exposed portions during development, and the sensitivity and resolution were insufficient.

The acid-decomposable substance or the radiation-sensitive substance in the present invention has a functional group (dissolution inhibition site) capable of forming a hydrogen bond with two molecules of a carboxyl group. . By irradiation of radiation,
The radiation-sensitive substance generates a highly polar carboxyl group, and the dissolution inhibiting effect on the carboxyl polymer is lost.
That is, the solubility of the polymer having a carboxyl group in an alkaline solution is improved, and a positive image is obtained. On the other hand, in the acid-decomposable substance, a protective group is decomposed by an acid generated from an acid generator by irradiation with radiation, and a highly polar hydroxyl group or a carboxyl group is generated. Therefore, as in the case of the radiation-sensitive substance, the dissolution inhibiting effect on the carboxyl polymer disappears, the solubility in an alkaline solution is improved, and a positive image can be obtained. By using a novel acid-decomposable substance or a radiation-sensitive substance that strongly interacts with the carboxyl group of the polymer as described above, it is possible to realize high sensitivity and high resolution of a positive photoresist.

The present invention makes use of a high dissolution inhibiting effect on a carboxyl polymer of an acid-decomposable substance or a radiation-sensitive substance having a urea group or an aminopyrazine group. Therefore, as long as the substance to be combined with the carboxyl polymer has a urea skeleton and a 2-aminopyrazine skeleton, the acid-decomposable site and the radiation-sensitive site are not particularly limited.

In the formula (1), R ₁ and R _{2 each} have 3 to 3 carbon atoms.
50 organic groups, at least one of which has an acid-decomposable group. In the chemical formula 2, R ₃ and R _{4 each} have ₃ to ₄ carbon atoms.
0 organic group, at least one of which has an acid-decomposable group. In the chemical formula 3, R ₅ and R _{6 each} have 3 to 50 carbon atoms.
And at least one of them has a radiation-sensitive group. In Chemical Formula 4, R ₇ and R ₈ are organic groups having 3 to 40 carbon atoms, and at least one of them has a radiation-sensitive substance.

In (Chemical Formula 1), (Chemical Formula 3), (Chemical Formula 5), (Chemical Formula 6), (Chemical Formula 8) and (Chemical Formula 9), A ₁ , A ₃ , A ₅ , A ₈ , A ₁₄ , and A ₁₇ represent a carboxyl group. An atom capable of hydrogen bonding with two hydrogen atoms. Examples of the atom include an oxygen atom, a sulfur atom, a selenium atom, and a tellurium atom which are Group VI atoms of the periodic table. (1) (3) (5) (6) (8) (9)
Specific examples of the structure of the dissolution inhibiting site include urea and thiourea structures.

In (Chemical Formula 2), (Chemical Formula 4), (Chemical Formula 7) and (Chemical Formula 10), A ₂ , A ₄ , A ₁₂ and A ₂₁ are atoms capable of hydrogen bonding to one hydrogen atom of a carboxyl group. Examples of the atom include an oxygen atom, a nitrogen atom, and a sulfur atom. A ₁₃ , A ₂₂
Represents a methylene group. Specific structures of the dissolution inhibition sites of the above (Chemical Formula 2), (Chemical Formula 4), (Chemical Formula 7) and (Chemical Formula 10) include 2-aminopyrimidine, 2-aminooxazole, 2-aminothiazole, 2-aminoimidazole, and melamine. And the like.

In the present invention, (Chemical Formula 5) (Chemical Formula 6) (Chemical Formula 7)
In the formula, P _{1 to} P ₅ represent organic groups (acid-decomposable groups) that decompose by an acid-catalyzed reaction. This group is decomposed by an acid generated by irradiation with electromagnetic waves to generate a highly polar hydroxyl group and a carboxyl group, thereby improving the solubility of the polymer having a carboxyl group in an alkaline solution. As the acid-decomposable group, a t-butyl group, a 2-tetrahydrofuranyl group, a 2-tetrahydropyranyl group, a 1-ethoxyethyl group, and a trimethylsilyl group are preferable. The dissolution-promoting effect after exposure is greatly affected by the dissolution-inhibiting sites in the acid-decomposable substance and the proportions of t-butyl, 2-tetrahydrofuranyl, 2-tetrahydropyranyl, 1-ethoxyethyl, and trimethylsilyl groups. You. Therefore, (Formula 5) (Formula 6)
In Formula 7, a, b, d, and f are preferably 1 to 5. More preferably, it is 1-2. Also, e + g is desirably 1 to 5. More preferably, it is 2 to 4. h is preferably 0 to 5. More preferably, it is 0-1. When considering the dissolution inhibiting effect of the unexposed portion due to the dissolution inhibiting site, c is 1 to 10
Is desirable. More preferably, it is 1 to 5. (Formula 5)
In (Chem. 6) and (Chem. 7), A ₆ , A ₇ , A ₉ , A ₁₀ , and A ₁₁ are t-
It represents a butyl group, a 2-tetrahydrofuranyl group, a 2-tetrahydropyranyl group, a 1-ethoxyethyl group, a trimethylsilyl group, and a bonding group of a dissolution inhibiting site. Examples of the bonding group include an oxygen atom, a sulfur atom, an amino group and the like.

R ₉ , R ₁₀ , R ₁₁ or R ₁₃ represents an amino alcohol residue or an amino acid residue. Examples of the structure having a hydroxyl group and an amino group include 2-aminophenol, 3-aminophenol, 4-aminophenol, 2,3-diaminophenol, 2,4-diaminophenol, 4-aminoresorcinol, and 4,4'-diamino -3,3'-
Dihydroxybiphenyl, 3,3'-diamino-4,
4'-dihydroxybiphenyl, 2-aminoethanol, N-methyl-2-aminoethanol, 3-aminopropanol, 2-aminobutanol, 2-amino-3-
Methylbutanol, 4-aminobutanol, 5-aminopentanol, 6-aminohexanol, 2-aminocyclohexanol, 4-aminocyclohexanol, 2
-Aminoheptanol, 6-amino-2-methyl-2-
Heptanol, 8-aminooctanol, 10-aminodecanol, 12-aminododecanol, 1-amino-
2,3-propanediol, 2-amino-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol, bis-homotris, tris (hydroxymethyl) aminomethane, (3- (4 -Amino-phenyl) -adamantyl) methanol and the like.

Examples of the structure having an amino acid residue include glycine, alanine, phenylalanine, 2-aminopropionic acid, 3-aminobutylic acid, 4-aminopentanoic acid,
4-aminocyclohexanecarboxylic acid, 4-aminomethyl-cyclohexanecarboxylic acid, 2-aminobenzoic acid,
Examples thereof include 3-aminobenzoic acid, 4-aminobenzoic acid, and 4-aminomethylbenzoic acid.

In formula 6, R ₁₂ represents an isocyanate compound residue. Examples of the isocyanate include ethyl isocyanate, propyl isocyanate, butyl isocyanate, t-butyl isocyanate, hexyl isocyanate, cyclohexyl isocyanate, octyl isocyanate, dodecacyl isocyanate, 1-adamantyl isocyanate, phenyl isocyanate, 1-phenylethyl isocyanate, and benzyl isocyanate.
-Naphthylethyl isocyanate, 2,6-diisopropylphenylisocyanate, 1-biphenylisocyanate, 1,4-diisocyanatebutane, 1,6-diisocyanatehexane, 1,4-cyclohexanediisocyanate, 1,3-bis (isocyanatemethyl)
Cyclohexane, isophorodiisocyanate, 4,
4'-methylenebis (cyclohexyl isocyanate), 1- (1-naphthyl) ethyl isocyanate,
1,3-phenylene isocyanate, toluylene-2,
4-diisocyanate, 4,4'-methylenebis (phenylisocyanate), 4,4'-methylenebis (2,
6-diethylphenyl isocyanate), 1-adamantyl thioisocyanate and the like.

The acid-decomposable substance is used in an amount of 5 to the resin component.
It is desirable to add 〜100% by weight. More preferably, the content is 10 to 50% by weight. If it is less than 5%, the dissolution inhibiting effect is small, and the sensitivity and resolution are insufficient. If it is 100% or more, the film is brittle and the adhesion to the substrate is insufficient.

In the present invention, (Chemical Formula 8) (Chemical Formula 9) (Chemical Formula 1)
In 0), Q _{1 to} Q ₅ represent an orthoquinonediazide group and a diazodicarbonyl group. The orthoquinonediazide group and the diazodicarbonyl group generate a highly polar carboxyl group upon irradiation with an electromagnetic wave, and improve the solubility of the polymer having a carboxyl group in an alkaline solution. As the orthoquinonediazide group, a 1,2-naphthoquinone-2-diazide-4-sulfonyl group and a 1,2-naphthoquinone-2-diazide-5-sulfonyl group are preferable. Examples of the diazodicarbonyl group include a 2-diazo-1,3-dione group, a 2-diazo-1,3-diacyl group,
A 2-diazo-1-acyl-3-dione group is preferred. The dissolution accelerating effect after exposure is greatly affected by the dissolution inhibiting site in the photosensitive material and the ratio of orthoquinonediazide groups and diazodicarbonyl groups. Therefore, (Formula 8) (Formula 9) (Formula 10)
Among them, i, j, l, and n are preferably 1 to 5. More preferably, it is 1-2. Also, o + m is desirably 1 to 5. More preferably, it is 2 to 4. p is preferably from 0 to 5. More preferably, it is 0-1. In consideration of the dissolution inhibiting effect of the unexposed portion due to the dissolution inhibiting site, k is preferably 1 to 10. More preferably, it is 1 to 5. In (Chemical Formula 8), (Chemical Formula 9) and (Chemical Formula 10), A ₁₅ , A ₁₆ , A ₁₈ , A ₁₉ and A ₂₀ represent an orthoquinonediazide group, a bonding group of a diazodicarbonyl group and an aromatic group. Examples of the bonding group include an oxygen atom, a sulfur atom, an amino group and the like.

R ₁₄ , R ₁₅ , R ₁₆ or R ₁₈ represents an amine compound residue or an amino alcohol residue. Examples of the structure having two or more amino groups include 1,3-diaminobenzene,
1,4-diaminobenzene, 4,4'-diaminobiphenyl, 4,4'-diaminodiphenylmethane, 4,4 '
Diaminodiphenyl ether, 4,4'-diaminodiphenyl ketone, 4,4'-diaminodiphenylsulfone, 2,2-bis (4-aminophenyl) propane,
2,2-bis (4-aminophenyl) -1,1,1,
3,3,3-hexafluoropropane, bis (3-aminopropyl) tetramethyldisiloxane, 1,2,4-
Triaminobenzene, 1,3,5-triaminobenzene, 3,4,4'-triaminodiphenyl ether,
3,3 ', 4,4'-diaminobiphenyl, 3,3',
4,4'-tetraaminodiphenyl ether, 3,
3 ', 4,4'-tetraaminodiphenylsulfone,
1,2-diaminoethylene, N, N'-dimethyl-1,
2-diaminoethylene, 1,3-diaminopropane,
1,4-diaminobutane, N, N'-dimethyl-1,4
-Diaminobutane, 1,6-diaminohexane, 1,2
-Diaminocyclohexane, 1,4-diaminocyclohexane, 1,8-diaminooctane, 1,10-diaminodecane, 1,12-diaminododecane, 2-butyl-
2-ethyl-1,5-pentanediamine, 4-aminomethyl-1,8-diaminooctane, diethylenetriamine, bis (hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine and the like. Examples of the structure having a hydroxyl group and an amino group include 2-aminophenol, 3-aminophenol, 4-aminophenol, 2,3-diaminophenol, 2,4-diaminophenol, 4-aminoresorcinol, and 4,4'-
Diamino-3,3'-dihydroxybiphenyl, 3,
3'-diamino-4,4'-dihydroxybiphenyl,
2-aminoethanol, N-methyl-2-aminoethanol, 3-aminopropanol, 2-aminobutanol, 2-amino-3-methylbutanol, 4-aminobutanol, 5-aminopentanol, 6-aminohexanol, 2 -Aminocyclohexanol, 4-aminocyclohexanol, 2-aminoheptanol, 6-amino-2-methyl-2-heptanol, 8-aminooctanol, 10-aminodecanol, 12-aminododecanol, 1-amino- 2,3-propanediol, 2-
Amino-1,3-propanediol, 2-amino-2-
Ethyl-1,3-propanediol, bis-homotris, tris (hydroxymethyl) aminomethane, (3-
(4-amino-phenyl) -adamantyl) methanol and the like.

In the chemical formula 9, R ₁₇ represents a residue of an isocyanate compound. Examples of the isocyanate include ethyl isocyanate, propyl isocyanate, butyl isocyanate, t-butyl isocyanate, hexyl isocyanate, cyclohexyl isocyanate, octyl isocyanate, dodecacyl isocyanate, 1-adamantyl isocyanate, phenyl isocyanate, 1-phenylethyl isocyanate, and benzyl isocyanate.
-Naphthylethyl isocyanate, 2,6-diisopropylphenylisocyanate, 1-biphenylisocyanate, 1,4-diisocyanatebutane, 1,6-diisocyanatehexane, 1,4-cyclohexanediisocyanate, 1,3-bis (isocyanatemethyl)
Cyclohexane, isophorodiisocyanate, 4,
4'-methylenebis (cyclohexyl isocyanate), 1- (1-naphthyl) ethyl isocyanate,
1,3-phenylene isocyanate, toluylene-2,
4-diisocyanate, 4,4'-methylenebis (phenylisocyanate), 4,4'-methylenebis (2,
6-diethylphenyl isocyanate), 1-adamantyl thioisocyanate and the like.

The radiation-sensitive substance is used in an amount of 5 to the resin component.
It is desirable to add 〜100% by weight. More preferably, the content is 10 to 50% by weight. If it is less than 5%, the dissolution inhibiting effect is small, and the sensitivity and resolution are insufficient. If it is 100% or more, the film is brittle and the adhesion to the substrate is insufficient.

In the present invention, the alicyclic hydrocarbon structure of the carboxyl polymer is effective for improving the dry etch resistance of the resist film. Examples of the alicyclic structure in the carboxyl polymer include a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a norbornane ring, a tricyclodecane ring, a menthyl ring, a bornane ring, an adamantane ring, and a cholesteric ring. No.

The alicyclic structure is not particularly limited as long as it exists in at least one of the main chain and the side chain of the carboxyl polymer. Specific examples of the carboxyl polymer having an alicyclic hydrocarbon group in the main chain include poly (2-hydroxymethyl-5-norbornene), poly (2-carboxy-5-norbornene) and 2-hydroxymethyl-
5-norbornene-acrylic acid or / and acrylate copolymer, poly (2-carboxy-5-
Norbornene-acrylic acid or / and acrylate copolymer, 2-hydroxymethyl-5-norbornene-methacrylic acid or / and methacrylate copolymer, poly (2-carboxyl-5-norbornene-methacryl) Acids and / or methacrylic acid ester copolymers are exemplified.

Specific examples of the carboxyl polymer having an alicyclic hydrocarbon group in the side chain include polyacrylates, polymethacrylates, and acrylates.
An acrylic acid copolymer, a methacrylic acid ester-methacrylic acid copolymer, and the like are included.

In the present invention, when the carboxyl polymer has an alicyclic hydrocarbon structure and an organic group hydrolyzed by an alkali developing solution, swelling during development is small, and a high-resolution pattern can be obtained. Therefore, a high-resolution pattern having high dry etch resistance can be realized. Examples of the structure hydrolyzed by an alkali developer include a dicarboxylic anhydride structure, a lactone structure, a nitrophenyl ester structure, a methanesulfonylphenyl ester structure, a cyanomethyl ester structure, a trichloromethyl ester structure, and a methanesulfonylmethyl ester structure. .

Specific examples of the carboxyl polymer having an alicyclic hydrocarbon structure and an organic group hydrolyzed by an alkali developer include 2-hydroxymethyl-5-norbornene-maleic anhydride copolymer, 2-carboxyl -5-norbornene-maleic anhydride copolymer, 2-hydroxymethyl-5-norbornene-cyanomethyl acrylate copolymer, 2-hydroxymethyl-5-
Norbornene-cyanomethyl methacrylate copolymer, 2-carboxy-5-norbornene-cyanomethyl acrylate copolymer, 2-carboxy-5
-Norbornene-cyanomethyl methacrylate copolymer, 2-hydroxymethyl-5-norbornene-nitrophenyl acrylate copolymer, 2-hydroxymethyl-5-norbornene-nitrophenyl methacrylate copolymer, 2- Examples include carboxy-5-norbornene-acrylic acid nitrophenyl ester copolymer and 2-carboxy-5-norbornene-methacrylic acid nitrophenyl ester copolymer.

The radiation in the present invention includes ultraviolet light,
Far ultraviolet light such as KrF excimer laser light, vacuum ultraviolet light such as ArF excimer laser light, electron beam, X-ray, and the like are used. Therefore, as long as the substance generates an acid by the above-mentioned radiation, the substance that generates an acid by the radiation is not particularly limited. Examples of the substance that generates an acid upon irradiation include a diazonium salt, an iodonium salt, a sulfonium salt, a phosphonium salt, a sulfonate compound, a disulfone compound, a sulfonimide compound, and a diazomethane compound. Specific examples of these compounds include 4-N-
Phenylamino-2-methoxyphenyldiazonium sulfate, 4-N-phenylamino-2-methoxyphenyldiazonium-4-ethylphenylsulfate, diphenyliodonium triflate, diphenyliodonium hexafluoroantimonate, triphenylsulfonium triflate, triphenyl Phenylsulfonium hexafluoroantimonate, benzoin tosylate, pyrogallol methanesulfonic acid triester, diphenylsulfone, N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyl) Oxy) diphenylmaleimide, bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexyls) Honiru) diazomethane, bis (phenylene) diazomethane.

It is desirable that the substance generating an acid by the above-mentioned radiation be added in an amount of 0.01 to 50% by weight based on the resin component. More preferably, the content is 0.1 to 20% by weight. 0.01
% Or less, it is difficult to form a resist pattern with high sensitivity, and if it is 50% or more, the film is brittle and the adhesion to the substrate is insufficient.

The present invention relates to a method of mixing a carboxyl polymer having an alicyclic hydrocarbon structure and an organic group hydrolyzed by an alkali developer, a substance generating an acid by radiation, an acid-decomposable substance and a radiation-sensitive substance. Easily accomplished by: In the present invention, it goes without saying that it can be used in combination with a triplet sensitizer, an adhesion improver composed of various amine compounds, a surfactant and the like.

[0071]

BEST MODE FOR CARRYING OUT THE INVENTION

(Example 1) 2.64 g of glycine t-butyl ester
(0.02 mol) in dioxane (15 ml) at room temperature was added to 1.66 g of 1-4-cyclohexanediisocyanate.
(0.01 mol) are added. After stirring at 40 ° C. for 4 hours, dioxane (15 ml) is added to the reaction solution. Water (300
0 ml) to give 1,4-bis (3-
(T-butyloxycarbonylmethyl) ureidomethyl)
3.40 g (79%) of cyclohexane (Formula 11) was obtained.

[0072]

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2-carboxy-5-norbornene 6.9
1 g (0.05 mol), 2-t-butoxycarbonyl-5
-A solution of 9.72 g (0.05 mol) of norbornene, 9.81 g (0.1 mol) of maleic anhydride, and 1.28 g of 2,2'-azobis (isobutyronitrile) in tetrahydrofuran (1
20 g) was heated under reflux while introducing nitrogen to carry out polymerization for 8 hours. After the polymerization, the solution was poured into 500 ml of n-hexane, the polymer was precipitated and dried, and 2-carboxy-5-norbornene-2-t-butoxycarbonyl-5 was obtained.
As a result, 21.9 g of a norbornene-maleic anhydride copolymer (formula 12) was obtained (yield: 92%). When the molecular weight of this polymer in terms of polystyrene was determined in gel permeation chromatography (GPC) in tetrahydrofuran, the number average molecular weight was 5,500.

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100 parts by weight of the obtained copolymer, 1,4-bis (3- (t-butyloxycarbonylmethyl) ureidomethyl) cyclohexane (formula 11) synthesized above.
5 parts by weight of trimethylsulfonium triflate and 5 parts by weight of an acid generator were dissolved in 600 parts by weight of cyclohexanone, and filtered using a Teflon filter having a pore size of 0.20 μm to obtain a resist solution.

On a silicon substrate treated with hexamethyldisilazane, the above-mentioned resist solution was spin-coated, followed by heating at 80 ° C. for 2 minutes to form a resist film having a thickness of 0.50 μm. The substrate coated with the above-described resist was placed in an exposure experiment apparatus in which the inside of the apparatus was replaced with nitrogen, and a mask on which a pattern was drawn with chrome on a quartz plate was adhered thereon. ArF excimer laser light was irradiated through the mask, and after that, baking was performed at 80 ° C. for 2 minutes after exposure. Development was performed using an aqueous solution of tetramethylammonium hydroxide (0.
26N) at 23 ° C. for 120 seconds, followed by rinsing with pure water for 60 seconds. As a result, when the exposure amount was 20 mJ / cm ² , only the exposed portion of the resist film was dissolved and removed in the developing solution, and a positive 0.25 μm line and space pattern was obtained.

Example 2 14.1 g (0.06 mol) of 2-methyl-2-adamantyl methacrylate, 11.4 g (0.06 mol) of t-butyl methacrylate, 6.81 g (0.08 mol) of methacrylic acid, 2 A solution of 1.28 g of 2,2'-azobis (isobutyronitrile) in tetrahydrofuran (120 g) was heated under reflux while introducing nitrogen to carry out polymerization for 8 hours. After the polymerization, the solution was poured into 500 ml of n-hexane to precipitate and dry the polymer.
30.6 g of 2-adamantyl methacrylate-t-butyl methacrylate-methacrylic acid copolymer (formula 13)
(95% yield). When the molecular weight of this polymer in terms of polystyrene was examined in tetrahydrofuran by GPC, the number average molecular weight was 6,200.

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100 parts by weight of the obtained copolymer, Example 1
1,4-bis (3- (t-butyloxycarbonylmethyl) ureidomethyl) cyclohexane synthesized by
1) 20 parts by weight and 5 parts by weight of an acid generator trimethylsulfonium triflate were dissolved in 600 parts by weight of cyclohexanone, and filtered using a Teflon filter having a pore size of 0.20 μm to obtain a resist solution.

On a silicon substrate treated with hexamethyldisilazane, the above-mentioned resist solution was spin-coated, followed by heating at 80 ° C. for 2 minutes to form a resist film having a thickness of 0.48 μm. The substrate coated with the above-described resist was placed in an exposure experiment apparatus in which the inside of the apparatus was replaced with nitrogen, and a mask on which a pattern was drawn with chrome on a quartz plate was adhered thereon. ArF excimer laser light was irradiated through the mask, and after that, baking was performed at 80 ° C. for 2 minutes after exposure. Development was performed using an aqueous solution of tetramethylammonium hydroxide (0.
26N) at 23 ° C. for 120 seconds, followed by rinsing with pure water for 60 seconds. As a result, when the exposure amount was 40 mJ / cm ² , only the exposed portion of the resist film was dissolved and removed in the developing solution, and a positive 0.35 μm line and space pattern was obtained.

(Example 3) 6.91 g (0.05 mol) of 2-carboxy-5-norbornene, 9.72 g (0.05 mol) of 2-t-butoxycarbonyl-5-norbornene, 12.5 g of cyanomethyl methacrylate ( 0.1 mol), 2,
A solution of 1.28 g of 2'-azobis (isobutyronitrile) in tetrahydrofuran (120 g) was refluxed while heating while introducing nitrogen to carry out polymerization for 8 hours. After polymerization, n-
The solution was poured into 500 ml of hexane, the polymer was precipitated and dried, and 2-carboxy-5-norbornene-2-t was obtained.
26.5 g of -butoxycarbonyl-5-norbornene-cyanomethyl methacrylate copolymer (formula 14) was obtained (yield 91%). When the molecular weight of this polymer in terms of polystyrene was examined in tetrahydrofuran by GPC, the number average molecular weight was 8,000.

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100 parts by weight of the obtained copolymer, Example 1
1,4-bis (3- (t-butyloxycarbonylmethyl) ureidomethyl) cyclohexane synthesized by
1) 20 parts by weight and 5 parts by weight of an acid generator trimethylsulfonium triflate were dissolved in 600 parts by weight of cyclohexanone, and filtered using a Teflon filter having a pore size of 0.20 μm to obtain a resist solution.

The above resist solution was spin-coated on a silicon substrate treated with hexamethyldisilazane, and heated at 80 ° C. for 2 minutes to form a resist film having a thickness of 0.52 μm. The substrate coated with the above-described resist was placed in an exposure experiment apparatus in which the inside of the apparatus was replaced with nitrogen, and a mask on which a pattern was drawn with chrome on a quartz plate was adhered thereon. ArF excimer laser light was irradiated through the mask, and after that, baking was performed at 80 ° C. for 2 minutes after exposure. Development was performed using an aqueous solution of tetramethylammonium hydroxide (0.
26N) at 23 ° C. for 120 seconds, followed by rinsing with pure water for 60 seconds. As a result, when the exposure amount was 10 mJ / cm ² , only the exposed portion of the resist film was dissolved and removed in the developing solution, and a positive 0.20 μm line and space pattern was obtained.

Example 4 14.1 g (0.06 mol) of 2-methyl-2-adamantyl methacrylate, 7.51 g (0.06 mol) of cyanomethyl methacrylate, 6.89 g (0.08 mol) of methacrylic acid, A solution of 1.28 g of 2'-azobis (isobutyronitrile) in tetrahydrofuran (120 g) was heated under reflux while introducing nitrogen to carry out polymerization for 8 hours. After polymerization, n-hexane 500m
The polymer was precipitated and dried to give 2-methyl-2-adamantyl methacrylate-cyanomethyl methacrylate-methacrylic acid copolymer (Formula 15).
5.4 g were obtained (89% yield). When the molecular weight of this polymer in terms of polystyrene was examined in tetrahydrofuran by GPC, the number average molecular weight was 6,200.

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100 parts by weight of the obtained copolymer, Example 1
1,4-bis (3- (t-butyloxycarbonylmethyl) ureidomethyl) cyclohexane synthesized by
1) 20 parts by weight and 5 parts by weight of an acid generator trimethylsulfonium triflate were dissolved in 600 parts by weight of cyclohexanone, and filtered using a Teflon filter having a pore size of 0.20 μm to obtain a resist solution.

The above resist solution was spin-coated on a silicon substrate treated with hexamethyldisilazane, and heated at 80 ° C. for 2 minutes to form a resist film having a thickness of 0.47 μm. The substrate coated with the above-described resist was placed in an exposure experiment apparatus in which the inside of the apparatus was replaced with nitrogen, and a mask on which a pattern was drawn with chrome on a quartz plate was adhered thereon. ArF excimer laser light was irradiated through the mask, and after that, baking was performed at 80 ° C. for 2 minutes after exposure. Development was performed using an aqueous solution of tetramethylammonium hydroxide (0.
26N) at 23 ° C. for 120 seconds, followed by rinsing with pure water for 60 seconds. As a result, when the exposure amount was 15 mJ / cm ² , only the exposed portion of the resist film was dissolved and removed in the developing solution, and a positive 0.20 μm line and space pattern was obtained.

Example 5 2.64 g (0.02 mmol) of glycine t-butyl ester in dioxane (15 ml)
Add 2.50 cyclohexane isocyanate at room temperature to the solution.
g (0.02 mmol) are added. After stirring at 40 ° C. for 4 hours, dioxane (15 ml) is added to the reaction solution. By dropwise addition to water (3000 ml), 4.37 g (85%) of 1- (t-butyloxycarbonylmethyl-3-cyclohexylurea (Formula 16) was obtained.

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The 2-carboxy-5 synthesized in Example 1
100 parts by weight of norbornene-2-t-butoxycarbonyl-5-norbornene-maleic anhydride copolymer (Chemical formula 12), 1- (t-butyroxycarbonylmethyl-3-cyclohexylurea (Chemical formula 16) synthesized above) 5 parts by weight of trimethylsulfonium triflate and 5 parts by weight of an acid generator were dissolved in 600 parts by weight of cyclohexanone, and filtered using a Teflon filter having a pore size of 0.20 μm to obtain a resist solution.

On a silicon substrate treated with hexamethyldisilazane, the above-mentioned resist solution was spin-coated, followed by heating at 80 ° C. for 2 minutes to form a resist film having a thickness of 0.50 μm. The substrate coated with the above-described resist was placed in an exposure experiment apparatus in which the inside of the apparatus was replaced with nitrogen, and a mask on which a pattern was drawn with chrome on a quartz plate was adhered thereon. ArF excimer laser light was irradiated through the mask, and after that, baking was performed at 80 ° C. for 2 minutes after exposure. Development was performed using an aqueous solution of tetramethylammonium hydroxide (0.
26N) at 23 ° C. for 120 seconds, followed by rinsing with pure water for 60 seconds. As a result, when the exposure amount was 30 mJ / cm ² , only the exposed portion of the resist film was dissolved and removed in the developing solution, and a positive 0.25 μm line and space pattern was obtained.

Example 6 100 parts by weight of 2-methyl-2-adamantyl methacrylate-2-t-butoxycarbonyl-5-norbornene-methacrylic acid copolymer (Chem. 13) synthesized in Example 2 and Example 5 1- (t) synthesized by
20 parts by weight of butyroxycarbonylmethyl-3-cyclohexylurea (formula 16) and 5 parts by weight of an acid generator, trimethylsulfonium triflate, were dissolved in 600 parts by weight of cyclohexanone, and the solution was filtered through a Teflon filter having a pore size of 0.20 μm. A resist solution was used.

On a silicon substrate treated with hexamethyldisilazane, the above-mentioned resist solution was spin-coated, followed by heating at 80 ° C. for 2 minutes to form a resist film having a thickness of 0.51 μm. The substrate coated with the above-described resist was placed in an exposure experiment apparatus in which the inside of the apparatus was replaced with nitrogen, and a mask on which a pattern was drawn with chrome on a quartz plate was adhered thereon. ArF excimer laser light was irradiated through the mask, and after that, baking was performed at 80 ° C. for 2 minutes after exposure. Development was performed using an aqueous solution of tetramethylammonium hydroxide (0.
26N) at 23 ° C. for 120 seconds, followed by rinsing with pure water for 60 seconds. As a result, when the exposure amount was 40 mJ / cm ² , only the exposed portion of the resist film was dissolved and removed in the developing solution, and a positive 0.30 μm line and space pattern was obtained.

Example 7 100 parts by weight of the 2-carboxy-5-norbornene-2-t-butoxycarbonyl-5-norbornene-cyanomethyl methacrylate copolymer synthesized in Example 3 (Formula 14), Example 5 1 synthesized by
20 parts by weight of-(t-butyloxycarbonylmethyl-3-cyclohexylurea (formula 16) and 5 parts by weight of an acid generator trimethylsulfonium triflate were added to cyclohexanone 6
The resultant was dissolved in 00 parts by weight and filtered using a Teflon filter having a pore size of 0.20 μm to obtain a resist solution.

On a silicon substrate treated with hexamethyldisilazane, the above-mentioned resist solution was spin-coated, followed by heating at 80 ° C. for 2 minutes to form a resist film having a thickness of 0.55 μm. The substrate coated with the above-described resist was placed in an exposure experiment apparatus in which the inside of the apparatus was replaced with nitrogen, and a mask on which a pattern was drawn with chrome on a quartz plate was adhered thereon. ArF excimer laser light was irradiated through the mask, and after that, baking was performed at 80 ° C. for 2 minutes after exposure. Development was performed using an aqueous solution of tetramethylammonium hydroxide (0.
26N) at 23 ° C. for 120 seconds, followed by rinsing with pure water for 60 seconds. As a result, when the exposure amount was 25 mJ / cm ² , only the exposed portion of the resist film was dissolved and removed in the developing solution, and a positive 0.25 μm line and space pattern was obtained.

Example 8 2-methyl-2-adamantyl methacrylate-cyanomethyl methacrylate-methacrylic acid copolymer synthesized in Example 4 (Formula 15)
Parts by weight, 1- (t-butyroxycarbonylmethyl-3-cyclohexylurea (Chem. 16) 2 synthesized in Example 5
0 parts by weight and 5 parts by weight of an acid generator trimethylsulfonium triflate are dissolved in 600 parts by weight of cyclohexanone.
The solution was filtered using a Teflon filter having a pore size of 0.20 μm to obtain a resist solution.

The above resist solution was spin-coated on a silicon substrate treated with hexamethyldisilazane, and heated at 80 ° C. for 2 minutes to form a resist film having a thickness of 0.45 μm. The substrate coated with the above-described resist was placed in an exposure experiment apparatus in which the inside of the apparatus was replaced with nitrogen, and a mask on which a pattern was drawn with chrome on a quartz plate was adhered thereon. ArF excimer laser light was irradiated through the mask, and after that, baking was performed at 80 ° C. for 2 minutes after exposure. Development was performed using an aqueous solution of tetramethylammonium hydroxide (0.
26N) at 23 ° C. for 120 seconds, followed by rinsing with pure water for 60 seconds. As a result, when the exposure amount was 25 mJ / cm ² , only the exposed portion of the resist film was dissolved and removed in the developing solution, and a positive 0.25 μm line and space pattern was obtained.

Example 9 A solution of 2.30 g (0.02 mol) of 4-aminocyclohexanol in dioxane (10 ml)
And 4.80 g of di-t-butyl dicarbonate at 15 ° C.
(0.022 mmol) in dioxane (4 ml) was added dropwise and stirred at room temperature for 1 hour. After evaporating the solvent under reduced pressure, dioxane (10 ml) and 5.64 g (0.021 mol) of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride are added. 5.6 m of triethylamine was added to the reaction solution at 15 ° C.
1 (0.04 mol) was added dropwise, the mixture was stirred at room temperature for 30 minutes, and the reaction solution was filtered. After evaporating the solvent under reduced pressure, methylene chloride (20 ml) and trifluoroacetic acid (20 ml) are added at room temperature, and the mixture is stirred for 20 minutes. After evaporating the solvent under reduced pressure, ether (6
0 ml) is added. The precipitate is ground and then filtered. The obtained solid was dissolved in methylene chloride (400 ml), and saturated aqueous sodium bicarbonate (400 ml × 3) and water (400 ml).
Wash with. The solvent was distilled off under reduced pressure to give 4- (1,
2-naphthoquinone-2-diazide-5-sulfoxy)
5.78 g (83%) of cyclohexylamine (pACQ)
Obtained.

3.95 g (0.02 m) of the pACQ synthesized above
ol) in dioxane (15 ml) at room temperature is added with 2.50 g (0.02 mol) of cyclohexane isocyanate. After stirring at 40 ° C for 4 hours, dioxane (15
ml) is added. 4.97 g (77%) of 1-cyclohexyl-3- (4- (1,2-naphthoquinone-2-diazido-5-sulfoxy) cyclohexyl) urea (Formula 17) was added dropwise to water (3000 ml). )Obtained.

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2-carboxy-5-norbornene 13.
82 g (0.10 mol), 9.81 g of maleic anhydride (0.10 mol)
1 mol), 2,2'-azobis (isobutyronitrile)
1.28 g of a tetrahydrofuran solution (120 g)
The mixture was heated under reflux while introducing nitrogen, and polymerized for 8 hours. After the polymerization, the solution was poured into 500 ml of n-hexane, and the polymer was precipitated and dried to obtain 2-carboxy-5-norbornene-maleic anhydride copolymer (Chem. 18).
3 g was obtained (yield 90%). When the molecular weight of this polymer in terms of polystyrene was examined in tetrahydrofuran by GPC, the number average molecular weight was 7,400.

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100 parts by weight of the obtained copolymer, 1-cyclohexyl-3- (4- (1,2-naphthoquinone-2-diazide-5-sulfoxy) cyclohexyl) urea (Formula 17) synthesized above. Parts by weight were dissolved in 600 parts by weight of cyclohexanone and filtered using a Teflon filter having a pore size of 0.20 μm to obtain a resist solution.

The above-mentioned resist solution was spin-coated on a silicon substrate treated with hexamethyldisilazane, and then heated at 80 ° C. for 2 minutes to form a resist film having a thickness of 0.53 μm. The substrate coated with the above-described resist was placed in an exposure experiment apparatus in which the inside of the apparatus was replaced with nitrogen, and a mask on which a pattern was drawn with chrome on a quartz plate was adhered thereon. ArF excimer laser light was irradiated through the mask. The development was performed with an aqueous solution of tetramethylammonium hydroxide (0.26 N) at 23 ° C. for 120 seconds, followed by rinsing with pure water for 60 seconds. As a result, the exposure amount is 50 m
At J / cm ² , only the exposed portions of the resist film were dissolved and removed in the developing solution, and a positive 0.30 μm line and space pattern was obtained.

Example 10 23.5 g (0.10 mol) of 2-methyl-2-adamantyl methacrylate, 8.61 g (0.10 mol) of methacrylic acid, 1,2'-azobis (isobutyronitrile) 1. 28 g of a tetrahydrofuran solution (120 g) was heated under reflux while introducing nitrogen to obtain a solution of 8 g.
Polymerization was carried out for hours. After the polymerization, the solution was poured into 500 ml of n-hexane, and the polymer was precipitated and dried to obtain 30.5 g of 2-methyl-2-adamantyl methacrylate-methacrylic acid copolymer (formula 19) (yield: 95%). . GP
When the molecular weight of this polymer in terms of polystyrene was examined in tetrahydrofuran by C, the number average molecular weight was 6
It was 200.

[0107]

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100 parts by weight of the obtained copolymer, Example 9
1-cyclohexyl-3- (4- (1,2-
30 parts by weight of naphthoquinone-2-diazide-5-sulfoxy) cyclohexyl) urea (formula 17) was dissolved in 600 parts by weight of cyclohexanone, and filtered using a Teflon filter having a pore size of 0.20 μm to obtain a resist solution. The above resist solution was spin-coated on a silicon substrate treated with hexamethyldisilazane, and then heated at 80 ° C. for 2 minutes to form a resist film having a thickness of 0.50 μm. The substrate coated with the above-described resist was placed in an exposure experiment apparatus in which the inside of the apparatus was replaced with nitrogen, and a mask on which a pattern was drawn with chrome on a quartz plate was adhered thereon. ArF excimer laser light was irradiated through the mask. Development was performed using an aqueous solution of tetramethylammonium hydroxide (0.26
N) at 23 ° C. for 120 seconds, followed by rinsing with pure water for 60 seconds. As a result, when the exposure amount is 60 mJ / cm ² , only the exposed portion of the resist film is dissolved and removed in the developing solution,
A positive 0.30 μm line and space pattern was obtained.

(Example 11) 13.8 g (0.10 mol) of 2-carboxy-5-norbornene, 12.5 g (0.1 mol) of cyanomethyl methacrylate, 2,2'-azobis
A solution of 1.28 g of (isobutyronitrile) in tetrahydrofuran (120 g) was refluxed under heating while introducing nitrogen to carry out polymerization for 8 hours. After polymerization, n-hexane 500
The solution was poured into the solution, and the polymer was precipitated and dried.
24.7 g of a carboxy-5-norbornene-cyanomethyl methacrylate copolymer (formula 20) was obtained (yield 94).
%).

When the molecular weight of this polymer in tetrahydrofuran was determined by GPC, the number average molecular weight was 7,100.

[0111]

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100 parts by weight of the obtained copolymer, Example 9
1-cyclohexyl-3- (4- (1,2-
30 parts by weight of naphthoquinone-2-diazide-5-sulfoxy) cyclohexyl) urea (formula 17) was dissolved in 600 parts by weight of cyclohexanone, and filtered using a Teflon filter having a pore size of 0.20 μm to obtain a resist solution. The above resist solution was spin-coated on a silicon substrate treated with hexamethyldisilazane, and then heated at 80 ° C. for 2 minutes to form a resist film having a thickness of 0.49 μm. The substrate coated with the above-described resist was placed in an exposure experiment apparatus in which the inside of the apparatus was replaced with nitrogen, and a mask on which a pattern was drawn with chrome on a quartz plate was adhered thereon. ArF excimer laser light was irradiated through the mask. Development was performed using an aqueous solution of tetramethylammonium hydroxide (0.26
N) at 23 ° C. for 120 seconds, followed by rinsing with pure water for 60 seconds. As a result, when the exposure amount is 40 mJ / cm ² , only the exposed portion of the resist film is dissolved and removed in the developing solution,
A positive 0.20 μm line and space pattern was obtained.

(Example 12) 2-methyl-2-adamantyl methacrylate-cyanomethyl methacrylate-methacrylic acid copolymer (Chemical Formula 15) synthesized in Example 4
0 parts by weight, 1-cyclohexyl-3 synthesized in Example 9
-(4- (1,2-Naphthoquinone-2-diazide-5
Sulfoxy) cyclohexyl) urea
Parts by weight were dissolved in 600 parts by weight of cyclohexanone and filtered using a Teflon filter having a pore size of 0.20 μm to obtain a resist solution.

The above resist solution was spin-coated on a silicon substrate treated with hexamethyldisilazane, and then heated at 80 ° C. for 2 minutes to form a resist film having a thickness of 0.53 μm. The substrate coated with the above-described resist was placed in an exposure experiment apparatus in which the inside of the apparatus was replaced with nitrogen, and a mask on which a pattern was drawn with chrome on a quartz plate was adhered thereon. ArF excimer laser light was irradiated through the mask. The development was performed with an aqueous solution of tetramethylammonium hydroxide (0.26 N) at 23 ° C. for 120 seconds, followed by rinsing with pure water for 60 seconds. As a result, the exposure amount is 45 m
At J / cm ² , only the exposed portion of the resist film was dissolved and removed in the developing solution, and a positive 0.25 μm line and space pattern was obtained.

Example 13 1,2-Naphthoquinone-2
-Diazide-5-sulfonyl chloride 10.8 g (0.0
4 mol), 2-t-butoxycarbonylamino-4,6
To a solution of 4.00 g (0.20 mol) of dihydroxypyrimidine in 50 ml of dioxane was added dropwise 6.7 ml (0.12 mol) of triethylamine at 10 ° C., and the mixture was stirred at room temperature for 3 hours. After filtration, the filtrate is added dropwise to a 1N aqueous hydrochloric acid solution (2 L) to obtain a solid. At room temperature, methylene chloride (10 ml) and trifluoroacetic acid (10 m
Add l) and stir for 20 minutes. After evaporating the solvent under reduced pressure, ether (30 ml) is added. The precipitate is ground and then filtered. The obtained solid is dissolved in methylene chloride (200 ml) and washed with saturated aqueous sodium bicarbonate (200 ml × 3) and water (200 ml). The solvent was distilled off under reduced pressure to obtain 7.69 g (65%) of 2-amino-4,6-bis (1,2-naphthoquinone-2-diazido-5-sulfoxy) pyrimidine (Formula 21).

2-carboxy-5 synthesized in Example 9
Norbornene-maleic anhydride copolymer (Formula 18) 10
0 parts by weight, and 30 parts by weight of the above synthesized 2-amino-4,6-bis (1,2-naphthoquinone-2-diazido-5-sulfoxy) pyrimidine (formula 21) were dissolved in 600 parts by weight of cyclohexanone, and the pore size was adjusted to 0. The solution was filtered using a .20 μm Teflon filter to obtain a resist solution.

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The above resist solution was spin-coated on a silicon substrate treated with hexamethyldisilazane, and heated at 80 ° C. for 2 minutes to form a resist film having a thickness of 0.50 μm. The substrate coated with the above-described resist was placed in an exposure experiment apparatus in which the inside of the apparatus was replaced with nitrogen, and a mask on which a pattern was drawn with chrome on a quartz plate was adhered thereon. ArF excimer laser light was irradiated through the mask. The development was performed with an aqueous solution of tetramethylammonium hydroxide (0.26 N) at 23 ° C. for 120 seconds, followed by rinsing with pure water for 60 seconds. As a result, the exposure amount was 40 m
At J / cm ² , only the exposed portions of the resist film were dissolved and removed in the developing solution, and a positive 0.25 μm line and space pattern was obtained.

(Example 14) 2-Synthesized in Example 10
100 parts by weight of a methyl-2-adamantyl methacrylate-methacrylic acid copolymer (Chemical Formula 19), 2-amino-4,6-bis (1,2-naphthoquinone-2-diazide-5-sulfoxy) synthesized in Example 13. Pyrimidine (Chemical 2
1) 30 parts by weight were dissolved in 600 parts by weight of cyclohexanone, and filtered using a Teflon filter having a pore size of 0.20 μm to obtain a resist solution.

The above-mentioned resist solution was spin-coated on a silicon substrate treated with hexamethyldisilazane, and then heated at 80 ° C. for 2 minutes to form a resist film having a thickness of 0.50 μm. The substrate coated with the above-described resist was placed in an exposure experiment apparatus in which the inside of the apparatus was replaced with nitrogen, and a mask on which a pattern was drawn with chrome on a quartz plate was adhered thereon. ArF excimer laser light was irradiated through the mask. The development was performed with an aqueous solution of tetramethylammonium hydroxide (0.26 N) at 23 ° C. for 120 seconds, followed by rinsing with pure water for 60 seconds. As a result, the exposure amount was 60 m
At J / cm ² , only the exposed portion of the resist film was dissolved and removed in the developing solution, and a positive 0.35 μm line and space pattern was obtained.

(Example 15) 2-Synthesized in Example 11
100 parts by weight of a carboxy-5-norbornene-cyanomethyl methacrylate copolymer (Chemical Formula 20), 2-amino-4,6-bis (1,2-naphthoquinone-2-diazide-5-sulfoxy) synthesized in Example 13 30 parts by weight of pyrimidine (chemical formula 21) was dissolved in 600 parts by weight of cyclohexanone, and filtered using a Teflon filter having a pore size of 0.20 μm to obtain a resist solution.

The above-mentioned resist solution was spin-coated on a silicon substrate treated with hexamethyldisilazane, and then heated at 80 ° C. for 2 minutes to form a resist film having a thickness of 0.50 μm. The substrate coated with the above-described resist was placed in an exposure experiment apparatus in which the inside of the apparatus was replaced with nitrogen, and a mask on which a pattern was drawn with chrome on a quartz plate was adhered thereon. ArF excimer laser light was irradiated through the mask. The development was performed with an aqueous solution of tetramethylammonium hydroxide (0.26 N) at 23 ° C. for 120 seconds, followed by rinsing with pure water for 60 seconds. As a result, the exposure amount is 45 m
At J / cm ² , only the exposed portion of the resist film was dissolved and removed in the developing solution, and a positive 0.25 μm line and space pattern was obtained.

(Example 16) 2-methyl-2-adamantyl methacrylate-cyanomethyl methacrylate-methacrylic acid copolymer (Chem. 15) synthesized in Example 4
0 parts by weight, 2-amino-4,6- synthesized in Example 13
30 parts by weight of bis (1,2-naphthoquinone-2-diazido-5-sulfoxy) pyrimidine (formula 21) was dissolved in 600 parts by weight of cyclohexanone, and filtered using a Teflon filter having a pore size of 0.20 μm to obtain a resist solution.

The above resist solution was spin-coated on a silicon substrate treated with hexamethyldisilazane, and heated at 80 ° C. for 2 minutes to form a resist film having a thickness of 0.50 μm. The substrate coated with the above-described resist was placed in an exposure experiment apparatus in which the inside of the apparatus was replaced with nitrogen, and a mask on which a pattern was drawn with chrome on a quartz plate was adhered thereon. ArF excimer laser light was irradiated through the mask. The development was performed with an aqueous solution of tetramethylammonium hydroxide (0.26 N) at 23 ° C. for 120 seconds, followed by rinsing with pure water for 60 seconds. As a result, the exposure amount was 40 m
At J / cm ² , only the exposed portion of the resist film was dissolved and removed in the developing solution, and a positive 0.25 μm line and space pattern was obtained.

Comparative Example 1 In Example 1, 1,4-bis (3- (t-butyloxycarbonylmethyl) ureidomethyl) cyclohexane (formula 1) which is an acid-decomposable substance was used.
A resist solution was obtained in exactly the same manner except that 1) was not used. The above resist solution is spin-coated on a silicon substrate treated with hexamethyldisilazane,
For 2 minutes to form a resist film having a thickness of 0.50 μm. The substrate coated with the above-described resist was placed in an exposure experiment apparatus in which the inside of the apparatus was replaced with nitrogen, and a mask on which a pattern was drawn with chrome on a quartz plate was adhered thereon. ArF excimer laser light is passed through the mask for 50 times.
mJ / cm ^{2 was} irradiated. When development was performed at 23 ° C. for 120 seconds in an aqueous solution of tetramethylammonium hydroxide (0.26 N), the entire film was dissolved, and a positive pattern could not be obtained.

(Comparative Example 2) In Example 9, 1-cyclohexyl-3- (4- (1,2-
Instead of 30 parts by weight of naphthoquinone-2-diazido-5-sulfoxy) cyclohexyl) urea (formula 17),
A resist solution was obtained in exactly the same manner except that 5 parts by weight of the acid generator trimethylsulfonium triflate was used.
On a silicon substrate treated with hexamethyldisilazane,
The above resist solution was spin-coated, and after the coating, heat-treated at 80 ° C. for 2 minutes to form a resist film having a thickness of 0.50 μm. The substrate coated with the above-described resist was placed in an exposure experiment apparatus in which the inside of the apparatus was replaced with nitrogen, and a mask on which a pattern was drawn with chrome on a quartz plate was adhered thereon. ArF excimer laser light is passed through the mask at 50 mJ / cm ^2.
Irradiated. Developing with an aqueous solution of tetramethylammonium hydroxide (0.26 N) at 23 ° C. for 120 seconds,
The entire film dissolved, and a positive pattern could not be obtained.

[0127]

The wavelength of the ArF excimer laser is 193 nm.
It is possible to provide a pattern forming method which is excellent in resolution performance without swelling while having a chemical structure which is transparent and has high dry etch resistance in a far ultraviolet region including the following.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Yoshiaki Okabe 7-1-1, Omika-cho, Hitachi City, Ibaraki Prefecture Within Hitachi Research Laboratory, Hitachi, Ltd.

Claims (12)

[Claims] 1. A carboxyl polymer having an alicyclic hydrocarbon structure, a substance which generates an acid by radiation, and (Where A ₁ is a group VI atom of the periodic table, R ₁ or R ₂
Is an organic group having 3 to 50 carbon atoms and has at least one of a hydroxyl group and / or a carboxyl group which is deprotected by an acid, and / or a compound represented by the following formula: 2] (Wherein A ₂ is an oxygen atom, a sulfur atom or a nitrogen atom,
₃ or R ₄ is an organic group having 3 to 40 carbon atoms, at least one of which has a hydroxyl group deprotected by an acid and / or a carboxyl group). Radiation-sensitive resin composition. 2. A carboxyl polymer having an alicyclic hydrocarbon structure, and (3) (Where A ₃ is an atom of Group VI of the periodic table, R ₅ or R ₆
Is a radiation-sensitive substance represented by an organic group having 3 to 50 carbon atoms), and / or (Chemical Formula 4) (Where A ₄ is an oxygen atom, a sulfur atom or a nitrogen atom,
₇ or R ₈ is an organic group having 3 to 40 carbon atoms, respectively.
A radiation-sensitive resin composition comprising a radiation-sensitive substance represented by the formula: 3. A carboxyl polymer having an alicyclic hydrocarbon structure and an organic group hydrolyzed in an alkali developing solution, a substance generating an acid by radiation, and (Where A ₁ is a group VI atom of the periodic table, R ₁ or R ₂
Is an organic group having 3 to 50 carbon atoms and has at least one of a hydroxyl group and / or a carboxyl group which is deprotected by an acid, and / or a compound represented by the following formula: 2] (Wherein A ₂ is an oxygen atom, a sulfur atom or a nitrogen atom,
₃ or R ₄ is an organic group having 3 to 40 carbon atoms, at least one of which has a hydroxyl group deprotected by an acid and / or a carboxyl group). Radiation-sensitive resin composition. 4. A carboxyl polymer having an alicyclic hydrocarbon structure and an organic group which is hydrolyzed by an alkali developing solution, and (Where A ₃ is an atom of Group VI of the periodic table, R ₅ or R ₆
Is a radiation-sensitive substance represented by an organic group having 3 to 50 carbon atoms), and / or (Chemical Formula 4) (Where A ₄ is an oxygen atom, a sulfur atom or a nitrogen atom,
₇ or R ₈ is an organic group having 3 to 40 carbon atoms, respectively.
A radiation-sensitive resin composition comprising a radiation-sensitive substance represented by the formula: (5) The compound of the formula (1) is a compound of the formula (5) (Where A ₅ is an oxygen atom or a sulfur atom, A ₆ and A
₇ is an oxygen atom or a carbonyloxy group,
₁ and P ₂ are each an acid-decomposable organic group, R ₉ or R ₁₀ is an alkyl group having 2 to 30 carbon atoms, an aryl group, an aralkyl group, a heterocyclic group, an alicyclic hydrocarbon group,
The radiation-sensitive resin composition according to claim 1, wherein the radiation-sensitive resin composition contains 1 to 100 parts by weight of a compound represented by the formula (a or b represents 1 to 5) based on 100 parts by weight of the total resin. (6) The compound of the formula (1) is a compound of the formula (6) (Where A ₈ is an oxygen atom or a sulfur atom, A ₉ is an oxygen atom or a carbonyloxy group, P ₃ is an acid-decomposable organic group,
R ₁₁ is an alkyl group, aryl group, aralkyl group, heterocyclic group, alicyclic hydrocarbon group having 2 to 30 carbon atoms, and R ₁₂ is an alkyl group, aryl group, aralkyl group, heterocyclic group having 2 to 30 carbon atoms. , Alicyclic hydrocarbon group, c is 1 to 10, d is 1 to 5
The radiation-sensitive resin composition according to claim 1 or 3, wherein (7) The compound of the formula (2) is a compound of the formula (7) (Where A ₁₀ or A ₁₁ is an oxygen atom or a carbonyloxy group, A ₁₂ is an oxygen atom, a sulfur atom or a nitrogen atom, A ₁₃ is a methylene group, and P ₄ or P ₅ is an acid-decomposable organic group, respectively. , R ₁₃ represents an alkyl group having 2 to 30 carbon atoms, an aryl group, an aralkyl group, a heterocyclic group, an alicyclic hydrocarbon group, e + g is 1 to 5, f is 1 to 5, h is 0 to 5) The radiation-sensitive resin composition according to claim 1, wherein: (8) The compound of the formula (3) is a compound of the formula (8) (Where A ₁₄ is an oxygen or sulfur atom, A ₁₅ and A
₁₆ is an oxygen atom or an amino group, Q ₁ and Q
₂ is a radiation-sensitive organic group; R ₁₄ or R ₁₅ is an alkyl group having 2 to 30 carbon atoms, an aryl group, an aralkyl group, a heterocyclic group, an alicyclic hydrocarbon group, i or j;
The radiation-sensitive resin composition according to claim 2, wherein the compound represented by the formula (1) represents 1 to 100 parts by weight based on 100 parts by weight of the total resin. (9) The compound of the formula (3) is a compound of the formula (9) (Where A ₁₇ is an oxygen atom or a sulfur atom, A ₁₈ is an oxygen atom or an amino group, Q ₃ is a radiation-sensitive organic group, R ₁₆ is an alkyl group having 2 to 30 carbon atoms, an aryl group, an aralkyl group,
A heterocyclic group, an alicyclic hydrocarbon group, R ₁₇ is an alkyl group having 2 to 30 carbon atoms, an aryl group, an aralkyl group, a heterocyclic group, an alicyclic hydrocarbon group, k is 1 to 10, and l is 1 to 5). The radiation-sensitive resin composition according to claim 2, wherein (10) The compound of the formula (4) is a compound of the formula (10) (Where A ₁₉ or A ₂₀ is an oxygen atom or an amino group, A ₂₁ is an oxygen atom, a sulfur atom or a nitrogen atom, A
₂₂ is a methylene group, Q ₄ or Q ₅ is a radiation-sensitive organic group, R ₁₈ is an alkyl group having 2 to 30 carbon atoms, an aryl group, an aralkyl group, a heterocyclic group, an alicyclic hydrocarbon group, m +
o is 1 to 5, n is 1 to 5, p is 0 to 5), and the radiation-sensitive resin composition according to claim 2 or 4, wherein 11. A step of applying and drying the radiation-sensitive resin composition according to claim 1 on a substrate, a step of irradiating an electromagnetic wave through a photomask, and a step of applying said radiation-sensitive resin composition to an alkaline developer. Forming a pattern by developing the pattern. 12. A step of applying and drying the radiation-sensitive resin composition according to claim 1 on a circuit forming surface or a protective film forming surface of an electronic circuit, irradiating an electromagnetic wave through a photomask, A method for producing an electronic device, comprising a step of developing a radiation-sensitive resin composition with an alkaline developer to form a pattern.