JP2847479B2 - Far ultraviolet resist composition and method for forming fine pattern using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resist composition used in the manufacture of semiconductor devices such as ICs and LSIs, and a method of forming a fine pattern using the same. For more information,
Deep UV light of 300 nm or less or KrF as an exposure energy source
Particularly useful for chemically amplified positive (or negative) resist composition when forming fine patterns on high-reflectivity substrates such as aluminum, polysilicon, aluminum-silicon, and tungsten silicide using excimer laser light (248.4 nm). And a method for forming a fine pattern using the same.

[0002]

2. Description of the Related Art In recent years, with the high density integration of semiconductor devices, the exposure apparatus used for fine processing, especially for photolithography, has been increasingly shortened in wavelength. At present, KrF excimer laser light (248.4 nm) and far ultraviolet light The use of the light source has been studied, and a large number of chemically amplified resist materials usable for this light source have been reported. When manufacturing a high-density integrated circuit using these light sources, a fine pattern is formed on various substrates using a chemically amplified resist material, but a highly reflective substrate such as aluminum, polysilicon, aluminum-silicon, or tungsten silicide is formed. Above, in the case of a normal chemically amplified resist material, a photosensitive phenomenon occurs in an unnecessary area due to reflection of light on a substrate surface or a step side surface, so-called notching,
Problems such as halation occur. In particular, far ultraviolet light (300 nm or less) or KrF excimer laser light (24 nm) having a shorter wavelength than conventional g-line (436 nm) or i-line (365 nm)
This problem is remarkable when 8.4 nm) is used. In order to solve this problem, it is considered to add a light absorber or a bleaching agent as in the case of a g-line resist or an i-line resist. However, when a light absorber is used, the light transmittance decreases, and as a result, The resolution performance becomes poor. Further, for example, a diazodiketo group [—COC (＝ N ₂ ) CO—] or a diazoketo group [—CO
When a bleaching agent having C (= N ₂ )-] is used, the sensitivity is extremely lowered, and neither of them can be used. On the other hand, EPC Publication Patent No. 543762 discloses phenoxymethylanthracene, anthracenemethanol, 9,
10-diphenylanthracene and the like are disclosed. However, these anthracene derivatives have poor solubility in solvents for resists, and have a problem that, even if dissolved, they precipitate during storage and cause particles. It cannot be used as an ultraviolet absorber. Accordingly, there is a current demand for a practical chemically amplified positive (or negative) resist composition capable of preventing halation or the like in such a short wavelength region.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and has been applied to a method of producing a deep ultraviolet light, a KrF excimer laser light, or the like on a highly reflective substrate having a step, such as aluminum, polysilicon, aluminum-silicon, or tungsten silicide. On the other hand, an object of the present invention is to provide a resist composition capable of suppressing halation and notching while maintaining high resolution performance and high sensitivity, and a method for forming a fine pattern using the same.

[0004]

In order to achieve the above object, the present invention comprises the following constitutions. "(1) The following (i) to (iii) (i) a resin which becomes alkali-soluble by removing a protecting group by the action of an acid, and (ii) a resin which becomes free of an alkali-soluble resin by the action of an acid. A combination of an alkali-soluble compound; and (iii) a combination of an alkali-soluble resin and a compound that cross-links the resin by the action of an acid to make the resin hardly alkali-soluble, and a photosensitivity that generates an acid upon exposure. A compound represented by the following general formula [1]

[0005]

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[Wherein, R ¹ is an alkyl group having 1 to 6 carbon atoms, a general formula [2]

[0007]

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(Wherein R ² is a hydrogen atom or a carbon number of 1 to 4)
R ³ represents an alkyl group having 1 to 6 carbon atoms, and m represents an integer of 0 to 3. ) Or a general formula [3]

[0009]

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(Wherein, R ⁴ represents an alkyl group having 1 to 6 carbon atoms, a phenyl group or a substituted phenyl group), and n represents an integer of 1 to 5. ] The resist composition characterized by comprising the anthracene derivative shown by these, and a solvent.

(2) (i) The above (1) is formed on a semiconductor substrate or the like.
Applying the resist composition described in 1 above, heating; (ii) exposing with deep ultraviolet light or KrF excimer laser light through a mask and, if necessary, performing a heat treatment; and (iii) alkali Developing with a developing solution. 』

That is, the present inventors have conducted intensive studies to achieve the above object, and as a result, the general formula [1]

[0013]

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(Wherein R ¹ and n are the same as those described above). A chemically amplified resist composition containing a compound represented by the formula ( ¹ ) as a far-ultraviolet light absorber for preventing halation or notching can achieve the above object. As a result, the present invention has been completed.

In the general formula [1], R ¹ has ¹ carbon atom.
Represents an alkyl group having 1 to 6 carbon atoms, a group represented by the general formula [2] or a group represented by the general formula [3], and the alkyl group having 1 to 6 carbon atoms includes a methyl group, an ethyl group, a propyl group and a butyl Group, amyl group, and hexyl group (which may be linear, branched, or cyclic).

In the general formula [2], R ² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ³ represents 1 carbon atom.
Represents an alkyl group of from 1 to 6, and has 1 to 1 carbon atoms represented by R ² .
Examples of the alkyl group 4 include a methyl group, an ethyl group, a propyl group, and a butyl group (which may be linear or branched).
Examples of the alkyl group having 1 to 6 carbon atoms represented by R ³ include a methyl group, an ethyl group, a propyl group, a butyl group, an amyl group, and a hexyl group (linear, branched, or cyclic). May be used.)

In the general formula [3], R ⁴ has 1 carbon atom.
Represents a phenyl group or a substituted phenyl group, wherein the alkyl group having 1 to 6 carbon atoms includes a methyl group,
Examples include an ethyl group, a propyl group, a butyl group, an amyl group, and a hexyl group (which may be linear, branched, or cyclic). And an alkyl group having 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a halogen atom.

Examples of the resin which is used in the present invention and becomes alkali-soluble by removing a protecting group by the action of an acid include, for example, the following general formula [4]

[0019]

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[Wherein, R ⁵ and R ⁸ each independently represent a hydrogen atom or a methyl group, and R ⁶ represents a tert-butoxycarbonyl group, a tert-butyl group, a tert-butoxycarbonylmethyl group, a 1-methylcyclohexyl An oxycarbonylmethyl group, a tetrahydropyranyl group, a 2-vinyloxyethyl group, a vinyloxymethyl group, an acetyl group, or the general formula [5]

[0021]

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(Wherein, R ¹⁰ represents a hydrogen atom or a methyl group, R ¹¹ represents a linear or branched alkyl group having 1 to 3 carbon atoms, and R ¹² represents a straight-chain or branched alkyl group having 1 to 6 carbon atoms. R ⁷ represents a hydrogen atom, a cyano group or a general formula [6].

[0023]

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(Wherein R ¹³ is a hydrogen atom, a halogen atom,
It represents a linear or branched alkyl group having 1 to 6 carbon atoms, a linear or branched alkoxy group having 1 to 6 carbon atoms, a tert-butoxycarbonyloxy group, or an acetyloxy group. R ⁹ represents a hydrogen atom, a cyano group, or —COOY (provided that Y represents a linear or branched alkyl group having 1 to 6 carbon atoms), and k and t represents a natural number each independently, j is 0 or a natural number (however,
0.2 <(k + j) / (k + t + j) <0.8 and j
Is a natural number, 0.05 ≦ j / (k + t + j) ≦ 0.50. ). ] The polymer shown by these is mentioned. Specific examples thereof include, for example, poly (p-tert-butoxystyrene / p-hydroxystyrene), poly (p-tert-butoxycarbonyloxystyrene / p-hydroxystyrene), and poly (p-tetrahydropyranyloxystyrene).
p-hydroxystyrene), poly (1-methoxy-1-methylethoxystyrene / p-hydroxystyrene), poly (p-hydroxystyrene)
1-ethoxyethoxystyrene / p-hydroxystyrene), poly (p-1-methoxyethoxystyrene / p-hydroxystyrene), poly (p-1-n-butoxyethoxystyrene / p-hydroxystyrene), poly (p- 1-isopropoxyethoxystyrene / p-hydroxystyrene), poly (p-1-ethoxyethoxystyrene / p-hydroxystyrene / p-acetyloxystyrene), poly [p-1- (1,1-dimethylethoxy)- 1-methylethoxystyrene / p-hydroxystyrene], poly (p-tert-butoxystyrene /
p-hydroxystyrene / methyl methacrylate), poly (p-1-ethoxyethoxystyrene / p-hydroxystyrene / fumaronitrile), poly (p-1-ethoxyethoxystyrene / p-hydroxystyrene / tert-butyl methacrylate), Poly (p-1-ethoxyethoxystyrene / p-hydroxystyrene / p-methylstyrene), poly (p-1-methoxyethoxystyrene / p-hydroxystyrene / p-tert)
-Butoxystyrene), poly (p-1-ethoxyethoxystyrene / p-hydroxystyrene / p-tert-butoxycarbonyloxystyrene), poly (p-1-methoxyethoxystyrene / p-hydroxystyrene / p-methylstyrene) , Poly [p- (2-vinyloxyethoxy) styrene /
p-hydroxystyrene], poly (p-vinyloxymethoxystyrene / p-hydroxystyrene), poly (p-1-methoxyethoxystyrene / p-hydroxystyrene / styrene), poly (p-1-ethoxyethoxystyrene / p -Hydroxystyrene / p-tert-butoxystyrene), poly (p-
1-ethoxyethoxystyrene / p-hydroxystyrene /
Styrene), poly (1-methylcyclohexyl p-vinylphenoxyacetate / p-hydroxystyrene), poly (tert-butyl p-vinylphenoxyacetate / p-hydroxystyrene), poly (tert-butyl p-vinylphenoxyacetate / p) -
Hydroxystyrene / methyl methacrylate) and the like.

Particularly preferred among the polymers represented by the general formula [4] are those wherein R ⁵ , R ⁸ and R ⁹ are hydrogen atoms;
R ⁶ is a group represented by the general formula [5] (wherein R ¹⁰ , R ¹¹ and R ¹² are the same as described above), and R ⁷ is a group represented by the general formula [6] (where R ¹³ is The same as the above.). Specific examples of these preferred polymers include, for example, poly (1-methoxy-1-methylethoxystyrene / p-hydroxystyrene), poly (p-1-ethoxyethoxystyrene / p-hydroxystyrene), poly (p-1 -Methoxyethoxystyrene / p-hydroxystyrene), poly (p-1-n-butoxyethoxystyrene / p-hydroxystyrene), poly (p-1-isopropoxyethoxystyrene / p-hydroxystyrene), poly (p- 1-ethoxyethoxystyrene / p-hydroxystyrene / p-acetyloxystyrene), poly [p-1- (1,1-dimethylethoxy) -1-methylethoxystyrene / p-hydroxystyrene], poly (p-1 -Ethoxyethoxystyrene / p-hydroxystyrene / p-methylstyrene), poly (p-1-methoxyethoxystyrene / p-hydroxystyrene / p-tert-)
Butoxystyrene), poly (p-1-methoxyethoxystyrene / p-hydroxystyrene / p-methylstyrene), poly (p-1-methoxyethoxystyrene / p-hydroxystyrene / styrene), poly (p-1-ethoxy) Ethoxystyrene / p-hydroxystyrene / p-tert-butoxystyrene), poly (p-1-ethoxyethoxystyrene / p-hydroxystyrene / p-tert-butoxycarbonyloxystyrene), poly (p-1-ethoxyethoxystyrene) / P-hydroxystyrene / styrene), poly (1-methylcyclohexyl p-vinylphenoxyacetate / p-hydroxystyrene), poly (tert-butyl p-vinylphenoxyacetate / p-
Hydroxystyrene) and the like.

As the alkali-soluble resin used in the present invention, for example, the following general formula [7]

[0027]

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[In the formula, R ¹⁴ represents a hydrogen atom or a methyl group, and R ¹⁵ represents a tert-butoxycarbonyl group, a tert-butoxycarbonylmethyl group, a tert-butyl group, a tetrahydropyranyl group, an acetyl group, or a compound represented by the general formula: [5]

[0029]

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(Wherein R ¹⁰ , R ¹¹ and R ¹² are the same as defined above), and R ¹⁶ is a hydrogen atom, a halogen atom, or a straight or branched chain having 1 to 6 carbon atoms. Represents an alkyl group, r represents a natural number, p and q each independently represent 0 or a natural number (provided that 0 ≦ (p + q) / (r + p + q)
≦ 0.2. ). ] The polymer shown by these is mentioned.

Specific examples of these polymers include, for example, poly (p-hydroxystyrene), poly (m-hydroxystyrene), poly (m-methyl-p-hydroxystyrene),
Poly (m-methyl-p-hydroxystyrene / p-hydroxystyrene), poly (p-tert-butoxystyrene / p-hydroxystyrene) [provided that the ratio of p-tert-butoxystyrene unit to p-hydroxystyrene unit is 2 ↓: Limited to 8 ↑. ], Poly (p-1-ethoxyethoxystyrene /
p-hydroxystyrene) [however, the ratio of p-1-ethoxyethoxystyrene units to p-hydroxystyrene units is 2
↓: Limited to 8 ↑. ], Poly (tert-butyl p-vinylphenoxyacetate / p-hydroxystyrene) [provided that
The ratio of the tert-butyl p-vinylphenoxyacetate unit to the p-hydroxystyrene unit is limited to 2 ↓: 8 ↑. ], Poly (p-1-ethoxyethoxystyrene / p-tert)
-Butoxystyrene / p-hydroxystyrene) [provided that
The ratio of p-1-ethoxyethoxystyrene unit and p-tert-butoxystyrene unit to p-hydroxystyrene unit is limited to 2 ↓: 8 ↓. ], Poly (p-tert-butoxystyrene / styrene / p-hydroxystyrene) [provided that
p-tert-butoxystyrene unit and styrene unit, and p-
The ratio of hydroxystyrene units is limited to 2 ↓: 8 ↑. And the like.

Particularly preferred among the polymers represented by the general formula [7] are those in which R ¹⁴ is a hydrogen atom and R ¹⁵ is tert.
- butyl group, an acetyl group, or the general formula [5] (wherein, R ^{1 0,} R ¹¹ and R ¹² are as defined above.) Is a polymer which is a group represented by the. Specific examples of these preferred polymers include, for example, poly (p-hydroxystyrene), poly (p-tert-butoxystyrene / p-hydroxystyrene) [provided that the ratio of p-tert-butoxystyrene units to p-hydroxystyrene units] Is limited to 2 ↓: 8 ↑. ], Poly (p-1-ethoxyethoxystyrene / p-hydroxystyrene) [however, the ratio of p-1-ethoxyethoxystyrene units to p-hydroxystyrene units is 2 ↓: 8 ↑]
Is limited to ], Poly (p-tert-butoxystyrene /
Styrene / p-hydroxystyrene) [However, the ratio of p-tert-butoxystyrene unit and styrene unit to p-hydroxystyrene unit is limited to 2 ↓: 8}. And the like.

Compounds which are used in the present invention and which become alkali-soluble by elimination of a protecting group by the action of an acid (hereinafter referred to as compounds)
Abbreviated as "dissolution inhibiting compound". ) Is represented by the following general formula [8]

[0034]

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[Wherein, R ¹⁷ is a tert-butoxycarbonyl group, a tert-butyl group, a tetrahydropyranyl group, a tert-butoxycarbonylmethyl group, a 1-methylcyclohexyloxycarbonylmethyl group, or a compound represented by the general formula [5]

[0036]

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(Wherein, R ¹⁰ , R ¹¹ and R ¹² are as defined above). A compound represented by the following general formula [9]:

[0038]

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Wherein R ¹⁷ is as defined above. Or various acetal compounds. Specific examples of these dissolution inhibiting compounds include, for example, 2,2-bis (4-tert-butoxyphenyl) propane, 2,2-bis (tetrahydropyranyloxyphenyl) propane, 2,2-bis [4- ( 1-ethoxyethoxy) phenyl] propane, 2,
2-bis [4- (1-methoxyethoxy) phenyl] propane, 2,2-bis [4- (1,1-dimethylethoxy) phenyl]
Propane, 2,2-bis [4- (1-ethoxyethoxycarbonylmethoxy) phenyl] propane, 2,2-bis (4-tert-
Butoxycarbonyloxyphenyl) propane, 2,2-bis (tert-butoxycarbonylmethoxyphenyl) propane, 1,1,2-tris (4-tert-butoxyphenyl) -2-
Methylpropane, 1,1,2-tris [4- (1-ethoxyethoxy) phenyl] -2-methylpropane, 1,1,2-tris (4-
tert-butoxycarbonylmethoxyphenyl) -2-methylpropane, 1,1,2-tris (tert-butoxycarbonyloxyphenyl) -2-methylpropane, 1,1,2-tris (1-benzyloxyethoxyphenyl)- 2-methylpropane, substituted or unsubstituted benzaldehyde acetal, substituted or unsubstituted benzaldehyde N, O-acetal,
Acetaldehyde acetal, acetaldehyde N,
O-acetal, propionaldehyde acetal, propionaldehyde N, O-acetal, butyraldehyde acetal, butyraldehyde N, O-acetal and the like can be mentioned.

The compound (hereinafter abbreviated as "crosslinkable compound") which is used in the present invention to crosslink with the resin by the action of an acid to make the resin hardly soluble in alkali (hereinafter, abbreviated as "crosslinkable compound") is represented by the following general formula [10]

[0041]

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[Wherein, R ¹⁸ represents a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, and R ¹⁹ represents a hydrogen atom or a general formula [11]

[0043]

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(Wherein, R ¹⁸ is the same as defined above). Or a compound represented by the following general formula [1]
2]

[0045]

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[Wherein, R ²⁰ is a hydrogen atom or a group having 1 to 1 carbon atoms.
6 linear represents a branched or cyclic alkyl group, R ²¹
Is a hydrogen atom or a general formula [13]

[0047]

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(Wherein R ²⁰ is the same as defined above). And the like. Specific examples of these crosslinkable compounds include, for example, 1,2,4-tris (cyclohexyloxymethoxy) benzene, 1,2,4-tris (isobutoxymethoxy) benzene, 1,2,4-tris (isopropoxymethoxy) ) Benzene, 1,3,5-tris (cyclohexyloxymethoxy) benzene, 1,3,5-tris (isobutoxymethoxy) benzene, 1,3,5-tris (isopropoxy) benzene, 1,3-bis ( Cyclohexyloxymethoxy) benzene, 1,3-bis (isobutoxymethoxy) benzene, 1,3-bis (isopropoxymethoxy) benzene, 1,4-bis (cyclohexyloxymethoxy) benzene, 1,4-bis (isobutoxy) Methoxy) benzene, 1,4-bis (isopropoxymethoxy) benzene,
2,4,6-tris (N, N-dimethoxymethylamino) -1,3,5-
Triazine, 2,4-bis (N, N-dimethoxymethylamino)
-1,3,5-triazine and the like.

As the photosensitive compound which generates an acid upon exposure (hereinafter abbreviated as "acid generator") used in the present invention, a resist pattern is formed from a photosensitive compound which generates an acid upon exposure literally. Any one may be used as long as it does not adversely affect the following. In the present invention, the following general formulas [14] and [1] are particularly preferable.
5], general formula [16], general formula [17] and general formula [1]
8] or a combination of these compounds.

[0050]

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[0051] [represents wherein, R ²² and R ²³ are independently a number of 1 to 6 straight, branched or cyclic alkyl group, a phenyl group, or a substituted phenyl group, R ²⁴ is a carbon Number 1
3 represents a linear or branched alkyl group. ]

[0052]

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[Wherein, R ²⁵ and R ²⁶ each independently represent a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, a phenyl group, or a substituted phenyl group. ]

[0054]

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[In the formula, R ²⁷ and R ²⁸ each independently represent a linear, branched or cyclic alkyl group, phenyl group or substituted phenyl group having 1 to 10 carbon atoms, and A represents a sulfonyl group. Or a carbonyl group. ]

[0056]

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[Wherein, R ²⁹ and R ³⁰ each independently represent a hydrogen atom, a halogen atom, or a linear or branched alkyl group having 1 to 4 carbon atoms, and R ³¹ represents 1 to 3 carbon atoms. 8 represents a perfluoroalkyl group. ]

[0058]

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Wherein R ³² and R ³³ each independently represent a hydrogen atom, a halogen atom or a nitro group, and R ³⁴ represents a trichloroacetyl group, a p-tosyl group, a p-trifluoromethylbenzenesulfonyl group, It represents a sulfonyl group or a trifluoromethanesulfonyl group. ]

Specific examples of the acid generator used in the present invention include, for example, 2-methanesulfonyl-2-methyl- (4-methylthio) propiophenone, 2-methyl-2-
(P-toluenesulfonyl) propiophenone, 2,4-dimethyl-2- (p-toluenesulfonyl) pentan-3-one,
2-cyclohexylcarbonyl-2- (p-toluenesulfonyl) propane, diphenyldisulfone, di (p-tolyl)
Disulfone, dicyclohexyldisulfone, bis (p-toluenesulfonyl) diazomethane, methylsulfonyl
p-toluenesulfonyldiazomethane, bis (2,4-dimethylbenzenesulfonyl) diazomethane, bis (p-chlorobenzenesulfonyl) diazomethane, bis (p-tert-butylbenzenesulfonyl) diazomethane, bisbenzenesulfonyldiazomethane, triphenylsulfonium.
Trifluoromethanesulfonate, diphenyl-p-tolylsulfonium perfluorooctanesulfonate,
Di (p-chlorophenyl) -p-tolylsulfonium trifluoromethanesulfonate, biscyclohexylsulfonyldiazomethane, bis (tert-butylsulfonyl)
Diazomethane, p-toluenesulfonyl-cyclohexylsulfonyldiazomethane, p-toluenesulfonyl-cyclohexylcarbonyldiazomethane, p-toluenesulfonic acid 2-nitrobenzyl, p-toluenesulfonic acid 2,6-dinitrobenzyl, p-trifluoromethylbenzenesulfonic acid 2,4-dinitrobenzyl and the like.

The resin according to the present invention, which is made alkali-soluble by removing a protecting group by the action of an acid, is disclosed, for example, in JP-A-4-2112.
No. 58 (US Pat. No. 5,350,660),
It can be easily obtained by the method described in 1259 (EPC Publication No. 476865) and the like.

The alkali-soluble resin and the crosslinkable compound according to the present invention can be easily obtained, for example, by the method described in EPC Publication No. 579420.

The compounds according to the present invention which are alkali-soluble by removing a protecting group by the action of an acid are described, for example, in JP-A-4-88.
It can be easily obtained by the method described in JP-A-348 or the like.

The acid generator according to the present invention is described in, for example,
No. 211258 (US Pat. No. 5,350,660),
It can be easily obtained by the methods described in JP-A-4-251259 (EPC Publication No. 476865) and JP-A-4-210960 (US Pat. No. 5,216,135).

As the solvent used in the present invention, any of the above (i) to (iii), an acid generator which generates an acid upon exposure, and a compound represented by the general formula [1] can be dissolved. Any material may be used as long as it is suitable, but usually a material having a good film-forming property is more preferably used. Specifically, methyl cellosolve acetate, ethyl cellosolve acetate,
Propylene glycol monomethyl ether acetate,
Propylene glycol monoethyl ether acetate,
Methyl lactate, ethyl lactate, 2-ethoxyethyl acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, N-methyl-2-pyrrolidone, cyclohexanone , Methyl ethyl ketone, 2-heptanone, 1,
Examples thereof include 4-dioxane, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, and ethylene glycol isopropyl ether, but are not limited thereto.

Specific examples of the compound represented by the general formula [1] (hereinafter sometimes abbreviated as “far-ultraviolet light absorber” of the present invention) used as a far-ultraviolet light absorber in the present invention. Examples include, for example, 9- (2-tert-butoxyethoxy)
Methylanthracene, 9- (2-n-butoxyethoxy) methylanthracene, 9- (2-isobutoxyethoxy) methylanthracene, 9- (2-isopropoxyethoxy) methylanthracene, 9- (2-ethoxyethoxy) methylanthracene , 9- (2-methoxyethoxy) methylanthracene, 9- (3-methoxybutoxy) methylanthracene, 9-
(1-methoxymethylpropoxy) methylanthracene,
9- (1-methoxymethylethoxy) methylanthracene,
2- (2-ethoxyethoxy) methylanthracene, 2- (2-
Methoxyethoxy) methylanthracene, 9- {3- (2-ethoxyethoxy) propyl} anthracene, 9- {3- (2-
(Methoxyethoxy) propyl dianthracene, 9-methoxymethylanthracene, 9-ethoxymethylanthracene, 9-isopropoxymethylanthracene, 9-methoxymethoxymethylanthracene, 9-anthrylmethyl acetate, 9-anthrylmethyl propionate, p- Examples thereof include 9-anthrylmethyl benzoate, 9-anthrylmethyl benzoate, and 9-anthrylpropyl acetate.

The compound represented by the general formula [1], which is used as a far-ultraviolet light absorber in the present invention, is exemplified by the following A:
~ Can be easily synthesized by Method C.

(Method A) The following general formula [19]

[0069]

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(Wherein n is as defined above) and 1 mole of the compound represented by the following general formula [20]

[0071]

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(Wherein R ¹ is the same as described above) and 0.5 to 100 moles of the compound represented by the formula (I) above, in the presence of an acid such as sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid or p-toluenesulfonic acid; The reaction is carried out in an organic solvent such as toluene, cyclohexane or the like at 20 to 150 ° C., preferably 50 to 130 ° C. for 0.5 to 10 hours with or without a solvent. The compound is easily obtained.

(Method B) 1 mol of the compound represented by the above general formula [19] is combined with a halogenating agent (for example, thionyl chloride,
Phosphorus oxychloride, phosphorus trichloride, phosphorus pentachloride, sulfuryl chloride,
Hydrogen chloride, hydrochloric acid, phosphorus oxybromide, phosphorus tribromide, phosphorus pentabromide,
Hydrogen bromide, hydrobromic acid, hydrogen iodide and the like. )
1 to 10 moles is stirred and reacted in a suitable solvent (for example, methylene chloride, benzene, toluene, n-hexane, etc.) at 20 to 150 ° C. for 0.5 to 10 hours, and post-treated according to a conventional method. The following general formula [21]

[0074]

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(Wherein, n is the same as described above) is obtained.

Then, 1 mol of the alkyl chloride compound represented by the above general formula [21] and 0.5 to 100 times by mol of the compound represented by the above general formula [20] are mixed with no catalyst or a base (for example, sodium hydroxide). , Potassium hydroxide, t
potassium tert-butoxide, sodium, potassium, sodium methoxide, sodium ethoxide, sodium hydride and the like. ) In a suitable solvent (including methylene chloride, benzene, toluene, n-hexane, xylene, tetrahydrofuran, etc.) in the presence of 20).
If the reaction is carried out by stirring at ~ 150 ° C for 0.5-20 hours and the reaction solution is post-treated according to a conventional method, the desired compound represented by the general formula [1] can be easily obtained.

(Method C) One mole of the compound represented by the above general formula [20] is combined with a halogenating agent (for example, thionyl chloride,
Phosphorus oxychloride, phosphorus trichloride, phosphorus pentachloride, sulfuryl chloride,
Hydrogen chloride, hydrochloric acid, phosphorus oxybromide, phosphorus tribromide, phosphorus pentabromide,
Hydrogen bromide, hydrobromic acid, hydrogen iodide and the like. )
The reaction solution is stirred for 1 to 10 times with a suitable solvent (eg, methylene chloride, benzene, toluene, n-hexane, etc.) at 20 to 150 ° C. for 0.5 to 10 hours, and the reaction solution is subjected to a conventional method. The following general formula [2]
2]

[0078]

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(Wherein, X represents a halogen atom, and R ¹ is the same as described above).

Next, 1 mol of the compound represented by the above general formula [22] and 1 mol of the compound 1 represented by the above general formula [19]
20-fold molar with a base (eg, sodium hydroxide, potassium hydroxide, sodium hydride, sodium methoxide, sodium ethoxide, potassium tert-butoxide,
Examples include triethylamine, diethylamine, pyridine, piperidine and the like. ) In a suitable solvent (including methylene chloride, benzene, toluene, xylene, tetrahydrofuran, 1,4-dioxane, etc.) in the presence of 20 to 15;
If the reaction is carried out at 0 ° C. for 0.5 to 10 hours with stirring and the reaction solution is post-treated according to a conventional method, the desired compound represented by the general formula [1] can be easily obtained.

The resist composition of the present invention usually comprises the above-mentioned four components (a resin which becomes alkali-soluble by the action of an acid, an acid generator, a deep ultraviolet light absorber and a solvent) or five components (an alkali-soluble resin, Inhibiting compounds, acid generators, far ultraviolet light absorbers and solvents, or alkali-soluble resins, crosslinkable compounds, acid generators, far ultraviolet light absorbers and solvents) as main components, but if necessary These may be added to a sensitivity adjuster [for example, basic resins such as polyvinylpyridine, poly (vinylpyridine / methyl methacrylate), poly (vinylpyridine / p-methylstyrene), and pyridine, piperidine, triethylamine, diethylamine, tetramethyl. Organic base compounds such as ammonium hydroxide are exemplified. And a plasticizer [for example, diethyl phthalate, dibutyl phthalate, dipropyl phthalate and the like]. ] And surfactants (for example, nonionic and fluorine-containing nonionic surfactants) can be added as appropriate.

In the resist composition of the present invention, the mixing ratio of the acid generator to the resin which becomes alkali-soluble by removing the protecting group by the action of an acid is as follows. Usually, it is about 1 to 30 parts by weight, preferably about 1 to 20 parts by weight.

In the resist composition of the present invention, the mixing ratio between the alkali-soluble resin and the dissolution inhibiting compound is as follows.
The dissolution inhibiting compound is usually 10 to 50 parts by weight, preferably about 15 to 40 parts by weight based on 100 parts by weight, and furthermore, the mixing ratio of the alkali-soluble resin and the dissolution inhibiting compound to the acid generator is alkali. The acid generator is usually 1 to 100 parts by weight of the total of the soluble resin and the dissolution inhibiting compound.
To 30 parts by weight, preferably about 1 to 20 parts by weight.

In the resist composition of the present invention, the mixing ratio of the alkali-soluble resin to the crosslinkable compound is usually 10 to 50 parts by weight per 100 parts by weight of the resin.
Parts by weight, preferably around 15 to 40 parts by weight, and further, as the mixing ratio of the alkali-soluble resin and the crosslinkable compound and the acid generator, the total of the alkali-soluble resin and the crosslinkable compound is 100 parts by weight. The acid generator is usually 1
To 30 parts by weight, preferably about 1 to 20 parts by weight.

The amount of the solvent in the resist composition of the present invention can be adjusted in the above three compositions [(i) + acid generator, (i)
i) + acid generator, and (iii) + acid generator], respectively, and dissolving each composition obtained by adding at least one kind of the far ultraviolet light absorber (compound represented by general formula [1]) according to the present invention. As a result, the amount is not particularly limited as long as it does not cause a problem when the obtained resist composition is coated on a substrate, but is usually alkali-soluble by removing a protecting group by the action of an acid. Resin, or the sum of alkali-soluble resin and dissolution inhibiting compound, or the sum of alkali-soluble resin and crosslinking compound, 100 to 2,000 parts by weight for each 100 parts by weight,
Preferably around 150 to 600 parts by weight is used.

The far ultraviolet light absorber according to the present invention may be added in an amount of 0.05 to 0.05 with respect to the resin of various resist components.
20% by weight, preferably 0.1 to 10% by weight.

The developing solution used in the above-mentioned various pattern forming methods may be any suitable developing solution which increases the dissolution rate difference between the exposed and unexposed areas according to the solubility of the resist composition. The concentration of the alkaline solution may be selected, and is usually selected from the range of 0.01 to 20%. Examples of the alkaline solution to be used include a solution containing organic amines such as tetramethylammonium hydroxide (TMAH), choline and triethanolamine, and inorganic alkalis such as NaOH and KOH. It is particularly preferred that the resist composition is developed using an existing aqueous solution of TMAH.

To form a pattern using the resist composition of the present invention, for example, the following may be performed.

The resist composition containing the far-ultraviolet light absorber according to the present invention is applied on a highly reflective substrate such as aluminum so as to have a thickness of about 0.5 to 2 μm (when used as an upper layer of three layers, 0.1 to 0.1 μm). 0.50.5 μm), and pre-baked in an oven at 70-130 ° C. for 10-30 minutes or on a hot plate at 70-130 ° C. for 1-2 minutes. Next, a mask for forming a target pattern is held over the above resist film, and a deep ultraviolet light of 300 nm or less or a KrF excimer laser light (248.4 nm) is irradiated so as to have an exposure amount of about 1 to 100 mJ / cm ^2. Then, if necessary, bake on a hot plate at 70 to 150 ° C. for 1 to 2 minutes. 0.1 ~
5% tetramethylammonium hydroxide (TMAH)
Using a developer such as an aqueous solution, soak for about 0.5 to 3 minutes (di
If development is performed by a conventional method such as a p) method, a puddle method, a spray method, or the like, a desired positive or negative pattern is formed on the substrate in a good shape.

[0090]

The resist composition according to the present invention is applied on a highly reflective substrate such as aluminum, polysilicon, aluminum-silicon, tungsten silicide or the like, and the resist film obtained is irradiated with deep ultraviolet light. Since light is absorbed as it passes through the resist film, the reflected wave from the highly reflective substrate becomes extremely weak, and as a result, light interference in the resist film is reduced. Further, the reflected light to the unexposed portion is easily absorbed. Therefore, the effects of halation and standing waves are reduced.

Further, at the exposed portion, far-ultraviolet light reaches an appropriate level to the lower layer of the resist film, so that acid is generated from the acid generator, and the chemical amplification action proceeds sufficiently, so that the resolution performance does not decrease.

The far ultraviolet light absorbent used in the resist composition according to the present invention has a diazoketo group, a diazodiketo group, When compared with a photosensitive compound having a diazodisulfonyl group or a diazoketosulfonyl group, a large amount of the disadvantages of these compounds, that is, a large decrease in sensitivity, and a small light absorption intensity around 250 nm are present. Need to be added, resulting in pattern shape,
Since it completely overcomes the drawbacks such as poor resolution performance, it is possible to form a good pattern even on a substrate with high reflection and steps, which could not be sufficiently achieved with the use of conventional compounds of this type. Enabled.

Further, the far-ultraviolet light absorber used in the resist composition according to the present invention has an extremely good solubility in a solvent. Therefore, even if the resist composition is stored for a long time, the existing anthracene derivative is used. There was no precipitate as seen in some cases, and it was possible to provide a practical resist composition for a highly reflective substrate. Hereinafter, the present invention will be described in more detail with reference to Synthesis Examples, Examples, and Comparative Examples, but the present invention is not limited by these.

[0094]

【Example】

Synthesis Example 1 Synthesis of 9- (2-methoxyethoxy) methylanthracene 1000 ml of 2-methoxyethanol was dissolved in 1500 ml of benzene, 3 ml of concentrated sulfuric acid was injected, and the mixture was heated to 80 ° C. Then, a solution of 45 g (0.22 mol) of 9-anthracenemethanol in 450 ml of 2-methoxyethanol was injected under reflux, and 1.5 g
The mixture was stirred and refluxed for hours. After standing at room temperature overnight, the extract was washed with a saturated aqueous solution of sodium hydrogen carbonate, dried over anhydrous magnesium sulfate, and then the solvent was distilled off. 63 g of a crude oily residue obtained was separated by column chromatography [filler: Wakogel C] -200 (trade name of Wako Pure Chemical Industries, Ltd.); eluent: n-hexane / ethyl acetate = 50/1 → 25/1 → 8/1
(V / V)] to give 47.6 g of 9- (2-methoxyethoxy) methylanthracene as an orange-yellow oil. _{^{1 HNMR δppm (CDCl 3):}} 3.37 (3H, s, C H 3 O), 3.53~
3.57 (2H, t, CH ₃ OC H _2- ), 3.73 to 3.77 (2H, t, CH ₃ O-CH _{2
C H 2 O), 5.55 (} 2H, s, Ar-C H 2 O -), 7.43~7.56 (4H, m,
Aromatic ring 2-H, 3-H, 6-H, 7-H), 7.99 (2H, d, J = 9Hz, Aromatic ring 4-
H, 5-H), 8.42 (2H, d, J = 9Hz, Aromatic ring 1-H, 8-H), 8.44 (1H,
s, aromatic ring 10-H). IR (Neat) νcm ^-1 : 1130. UV (CH ₃ CN) ε (λ = 248 nm): 8.85 × 10 ⁴ .

Synthesis Example 2 Synthesis of 9- (2-ethoxyethoxy) methylanthracene (1) 50 g (0.24 mol) of 9-anthracenemethanol was suspended in 50 ml of methylene chloride, and 32.3 g of thionyl chloride was added thereto.
g (0.27 mol) in benzene (300 ml) was injected.
The mixture was stirred and refluxed for hours. The reaction solution was poured into 500 ml of ice water,
The organic layer obtained by liquid separation was washed with water (100 ml × 3) and dried over anhydrous magnesium sulfate. After filtering off the drying agent, the solvent was distilled off to obtain 51.2 g of residual crude 9-chloromethylanthracene as an orange-yellow oil.

(2) 5.2 g (23 mmol) of the crude 9-chloromethylanthracene obtained in the above (1) and 300 ml of 2-ethoxyethanol were stirred and reacted at room temperature for 10 hours.
The mixture was poured into 300 ml, and extracted with methylene chloride (300 ml × 1). The organic layer was dried over anhydrous magnesium sulfate, the desiccant was filtered off, and the solvent was distilled off to obtain 2.75 g of a crude oily substance as a residue.
By column chromatography [filler: Wako gel C]
-200; eluent: n-hexane / ethyl acetate = 10/1]
1.52 g of 9- (2-ethoxyethoxy) methylanthracene was obtained as an orange-yellow oil. ¹ HNMR δ ppm (CDCl ₃ ): 1.21 to 1.26 (3H, t, CH ₃ CH ₂
O), 3.49~3.57 (2H, q , CH 3 C H 2 O), 3.59~3.63 (2H, t,
-OCH ₂ CH ₂ O-CH ₂ CH ₃ ), 3.76 to 3.80 (2H, t, -OC H ₂ CH ₂
-OCH ₂ CH ₃ ), 5.56 (2H, s, Ar-C H ₂ O-), 7.46 to 7.54 (4
H, m, aromatic ring 2-H, 3-H, 6-H, 7-H), 8.00 (2H, d, J = 8Hz, aromatic ring 4-H, 5-H), 8.43 (2H, d, J = 8Hz, aromatic ring 1-H, 8-H), 8.
46 (1H, s, aromatic ring 10-H). UV (CH ₃ CN) ε (λ = 248 nm): 8.34 × 10 ⁴ .

Synthesis Example 3 Synthesis of 9-ethoxymethylanthracene The crude 9-chloromethylanthracene obtained in (1) of Synthesis Example 2
After reacting 5.2 g (23 mmol) and 700 ml of ethanol with stirring at room temperature for 10 hours, the reaction solution was poured into 700 ml of water and extracted with methylene chloride (500 ml × 1). The organic layer was dried over anhydrous magnesium sulfate. The drying agent was filtered off, the solvent was distilled off, and 4.25 g of the crude crystal obtained as a residue was recrystallized from a 50% aqueous solution of tetrahydrofuran to obtain 4.02 g of 9-ethoxymethylanthracene as orange-yellow crystals. mp. 74-75 ° C. ¹ HNMR δ ppm (CDCl ₃ ): 1.25 to 1.30 (3H, t, CH ₃ CH ₂
O -), 3.73~3.75 (2H, q, CH 3 C H 2 O -), 5.46 (2H, s, A
_{rC H 2 O -), 7.45~7.54} (4H, m, aromatic ring 2-H, 3-H, 6-H, 7-
H), 8.00 (2H, d, J = 9Hz, aromatic ring 4-H, 5-H), 8.39 (2H, d,
J = 9Hz, aromatic ring 1-H, 8-H), 8.44 (1H, s, aromatic ring 10-H). IR (KBr tablet) νcm ^-1 : 1092. UV (CH ₃ CN) ε (λ = 248 nm): 8.09 × 10 ⁴ .

Synthesis Example 4 Synthesis of 9-anthrylmethyl acetate 15.0 g (72 mmol) of 9-anthracenemethanol was added to 7.3 g (72 mmol) of triethylamine and methylene chloride 1
Dissolved in 00 ml and 120 ml of 1,4-dioxane and cooled. Then 6.8 g (86.4 mmol) of acetyl chloride was added to 5-
The mixture was added dropwise at 10 ° C., and the mixture was stirred and reacted at the same temperature for 2.5 hours. After the reaction, the reaction solution was poured into 350 ml of ice water, made acidic with a 10% aqueous hydrochloric acid solution, and extracted with 100 ml of methylene chloride. The separated organic layer was washed once with 100 ml of water, and then with a saturated aqueous solution of sodium hydrogen carbonate.
After washing once with 100 ml, it was washed once with 100 ml of water and dried over anhydrous sodium sulfate. The drying agent was removed by filtration, and 17.7 g of crude crystals obtained by evaporating the solvent were recrystallized from n-hexane to give acetic acid
11.0 g of anthrylmethyl was obtained as yellow needles. m
p. 110.0-111.5 ° C. ¹ HNMR δppm (CDCl ₃ ): 2.07 (3H, s, CH ₃ COO-), 6.14
_{(2H, s, -COOC H 2} -), 7.45~7.60 (4H, m, aromatic ring 2H, 3-
H, 6-H, 7-H), 8.01 (2H, d, J = 8Hz, Aromatic ring 4-H, 5-H), 8.32
(2H, d, J = 8Hz, aromatic ring 1-H, 8-H), 8.49 (1H, s, aromatic ring 10
-H). IR (KBr tablet) νcm ^-1 : 1727. UV (CH ₃ CN) ε (λ = 248 nm): 9.81 × 10 ⁴ .

Synthesis Example 5 Synthesis of 9-anthrylmethyl propionate Using 7.4 g (79 mmol) of propanoyl chloride instead of acetyl chloride, the reaction and post-treatment were carried out in the same manner as in Synthesis Example 4, and 17.2 g of the obtained crude crystal was converted to n-hexane. To give 12.3 g of 9-anthrylmethyl propionate as yellow needles. mp. 79.0-80.0 ° C. ¹ HNMR δ ppm (CDCl ₃ ): 1.11 to 1.17 (3H, t, CH ₃ CH ₂
COO -), 2.31~2.39 (2H, q, CH 3 C H 2), 6.16 (2H, s, -COOC
H _2- ), 7.46 to 7.60 (4H, m, aromatic ring 2-H, 3-H, 6-H, 7-H),
8.02 (2H, d, J = 8Hz, Aromatic ring 4-H, 5-H), 8.33 (2H, d, J = 8H
z, aromatic ring 1-H, 8-H), 8.50 (1H, s, aromatic ring 10-H). IR (KBr tablet) νcm ^-1 : 1738. UV (CH ₃ CN) ε (λ = 248 nm): 9.82 × 10 ⁴ .

Synthesis Example 6 Synthesis of 9-anthrylmethyl p-methylbenzoate p-methylbenzoyl chloride instead of acetyl chloride 13.3
g (86 mmol) was reacted and worked up in the same manner as in Synthesis Example 4, and 25.1 g of the obtained crude crystals were recrystallized from n-hexane to give 9-anthrylmethyl p-methylbenzoate.
8.8 g were obtained as yellow needles. mp. 123.5-124.5
° C. ¹ H NMR δ ppm (CDCl ₃ ): 2.35 (3H, s, Ar-C H ₃ ), 6.37
(2H, s, -COOC H _2- ), 7.15 (2H, d, J = 8Hz, phenyl ring 3-
H, 5-H), 7.47 to 7.61 (4H, m, anthracene ring 2-H, 3-H, 6
-H, 7-H), 7.88 (2H, d, J = 8Hz, phenyl ring 2-H, 6-H), 8.0
5 (2H, d, J = 8Hz, anthracene ring 4-H, 5-H), 8.44 (2H, d,
J = 8Hz, anthracene ring 1-H, 8-H), 8.53 (1H, s, anthracene ring 10-H). IR (KBr tablet) νcm ^-1 : 1712. UV (CH ₃ CN) ε (λ = 248 nm): 1.09 × 10 ⁵ .

Synthesis Example 7 Synthesis of poly [p- (1-ethoxyethoxy) styrene / p-hydroxystyrene] (1) A catalytic amount of 2,2 ′ was added to 17.6 g of p-tert-butoxystyrene.
-Azobisisobutyronitrile was added, and a polymerization reaction was carried out in toluene at 80 ° C for 6 hours in a nitrogen stream. After cooling, the reaction solution was poured into 1000 ml of methanol and allowed to crystallize. The precipitated crystals were collected by filtration, washed with methanol, and dried under reduced pressure to obtain poly (p-te
(rt-butoxystyrene) 16.8 g was obtained as white powdery crystals. Weight average molecular weight about 10,000 (GPC method: polystyrene standard).

(2) 15.0 g of the poly (p-tert-butoxystyrene) obtained in the above (1) was dissolved in 1,4-dioxane, and concentrated hydrochloric acid was added.
10 ml was added and the mixture was stirred and refluxed for 4 hours. After cooling, the reaction solution was poured into 1000 ml of water for crystallization, and the precipitated crystals were collected by filtration, washed with water, and dried under reduced pressure to obtain 9.7 g of poly (p-hydroxystyrene) as white powder crystals.

(3) 4.0 g of the poly (p-hydroxystyrene) obtained in the above (2) and 1.2 g of ethyl vinyl ether were mixed with 1,4-
The mixture was dissolved in 35 ml of a mixture of dioxane and pyridine, a catalytic amount of p-toluenesulfonic acid was added thereto, and the mixture was stirred and reacted at room temperature for 24 hours. After the reaction, pour the reaction solution into 1000 ml of water,
After crystallization, the precipitated crystals are collected by filtration, washed with water, and dried under reduced pressure to obtain poly [p-
(1-ethoxyethoxy) styrene / p-hydroxystyrene] (5.0 g) was obtained as white powdery crystals. Of the resulting polymer
The composition ratio of p- (1-ethoxyethoxy) styrene unit to p-hydroxystyrene unit was about 4: 6 from ¹ HNMR measurement. Weight average molecular weight about 10,000 (GPC method: polystyrene standard).

Synthesis Example 8 Poly ｛p- [2- (2-methoxy)
Synthesis of (propoxy) styrene / p-hydroxystyrene} 4.0 g of poly (p-hydroxystyrene) obtained in (2) of Synthesis Example 7 and 4.8 g of 2-methoxy-1-propene were mixed with 1,4-
The mixture was dissolved in 35 ml of a mixture of dioxane and pyridine, a catalytic amount of sulfuric acid / pyridine salt was added thereto, and the mixture was stirred and reacted at room temperature for 20 hours. After the reaction, the reaction solution was poured into 1000 ml of water and crystallized, and the precipitated crystals were collected by filtration, washed with water, and dried under reduced pressure to obtain poly-p- [2-
(4.1 g) of (2-methoxy) propoxy] styrene / p-hydroxystyrene was obtained as white powdery crystals. P- [2- (2-methoxy) propoxy] styrene unit of the obtained polymer
The composition ratio of the p-hydroxystyrene unit was about 1: 1 from the result of ¹ HNMR measurement. Weight average molecular weight about 10,000 (GP
Method C: polystyrene standard).

Synthesis Example 9 Synthesis of poly (p-tert-butoxycarbonyloxystyrene / p-hydroxystyrene) (1) Using 22 g of p-tert-butoxycarbonyloxystyrene obtained according to the method described in U.S. Pat. No. 4,491,628 (1985). In the presence of a 2,2'-azobis (2,4-dimethylvaleronitrile) catalyst, in toluene, under a nitrogen stream, 90
The polymerization reaction was carried out at 4 ° C. for 4 hours. After cooling, the reaction solution was poured into methanol for crystallization, and the precipitated crystals were collected by filtration, washed with methanol, and dried under reduced pressure to obtain 15.2 g of poly (p-tert-butoxycarbonyloxystyrene) as white powder crystals. Weight average molecular weight: about 12000 (GPC method: polystyrene standard).

(2) 7.0 g of the poly (p-tert-butoxycarbonyloxystyrene) obtained in the above (1) was dissolved in 1,4-dioxane, 5 ml of concentrated hydrochloric acid was added, and the mixture was stirred and refluxed for 1.5 hours. After cooling, the reaction solution was poured into 1000 ml of water and allowed to crystallize,
The precipitated crystals were collected by filtration, washed with water, and dried under reduced pressure to obtain 4.8 g of poly (p-tert-butoxycarbonyloxystyrene / p-hydroxystyrene) as white powder crystals. Of the resulting polymer
The composition ratio of p-tert-butoxycarbonyloxystyrene unit to p-hydroxystyrene unit was about 1: 1 from the result of ¹ HNMR measurement. Weight average molecular weight 9500 (GPC
Method: polystyrene standard).

Synthesis Example 10 Synthesis of poly (tert-butyl p-vinylphenoxyacetate / p-hydroxystyrene) 4.0 g of poly (p-hydroxystyrene) obtained in (2) of Synthesis Example 7, 3.0 g of tert-butyl monochloroacetate and carbonic anhydride 2.8 g of potassium was suspended in 35 ml of acetone, and the mixture was refluxed with stirring for 2 hours. After cooling, the insolubles are filtered off,
The filtrate was poured into 1000 ml of water, crystallized, and the precipitated crystals were collected by filtration.
After washing with water and drying under reduced pressure, poly (p-vinylphenoxyacetic acid
(rt-butyl / p-hydroxystyrene) 5.2 g was obtained as white powdery crystals. The composition ratio of tert-butyl p-vinylphenoxyacetate unit and p-hydroxystyrene unit in the obtained polymer was about 1: 1 as determined by ¹ HNMR. Weight average molecular weight: about 11000 (GPC method: polystyrene standard).

Synthesis Example 11. Synthesis of poly [p- (1-ethoxyethoxy) styrene / p-hydroxystyrene / p-tert-butoxystyrene] (1) A catalytic amount of 2,2 ′ was added to 17.6 g of p-tert-butoxystyrene.
-Add azobis (methyl 2-methylpropionate)
The polymerization reaction was carried out in 1,4-dioxane under a nitrogen stream at 80 ° C. for 6 hours. After cooling the reaction solution, it was poured into 1000 ml of an aqueous methanol solution to cause crystallization, and the precipitated crystals were collected by filtration, washed with methanol,
After drying under reduced pressure, poly (p-tert-butoxystyrene) 16.7
g were obtained as white powder crystals. Weight average molecular weight about 20000
(GPC method: polystyrene standard).

(2) 15.0 g of the poly (p-tert-butoxystyrene) obtained in the above (1) was dissolved in 1,4-dioxane and concentrated hydrochloric acid was added.
20 ml was added and the mixture was stirred and reacted at 70 to 80 ° C. for 4 hours. After cooling, the reaction solution was poured into 1000 ml of water, crystallized, and the precipitated crystals were collected by filtration, washed with water, and dried under reduced pressure to obtain 11.0 g of poly (p-tert-butoxystyrene / p-hydroxystyrene) as white powder crystals. Was. The composition ratio of p-tert-butoxystyrene unit and p-hydroxystyrene unit in the obtained polymer was about 5:95 from ¹ HNMR measurement.

(3) 8.0 g of the poly (p-tert-butoxystyrene / p-hydroxystyrene) obtained in the above (2) and 2.0 g of ethyl vinyl ether were dissolved in 70 ml of 1,4-dioxane. Pyridinium p-toluenesulfonate was added and reacted with stirring at room temperature for 24 hours. After the reaction, water
Poured into 2000 ml, crystallized, and the precipitated crystals were collected by filtration, washed with water, and dried under reduced pressure to obtain poly [p- (1-ethoxyethoxystyrene / p-
Hydroxystyrene / p-tert-butoxystyrene] 9.6
g were obtained as white powder crystals. The composition ratio of (1-ethoxyethoxy) styrene unit to p-hydroxystyrene unit and p-tert-butoxystyrene unit in the obtained polymer was ¹ HNM.
It was about 35: 60: 5 from R measurement. Weight average molecular weight about 20
000 (GPC method: polystyrene standard).

Synthesis Example 12 Synthesis of poly [p- (1-ethoxyethoxy) styrene / p-hydroxystyrene / p-methylstyrene] (1) 100 g (0.567 mol) of p-tert-butoxystyrene and p
Synthesis Example 1 using 3.54 g (0.03 mol) of 1-methylstyrene
The reaction and post-treatment were carried out in the same manner as in 1 (1), and poly (p-
tert-butoxystyrene / p-methylstyrene) 92.3 g
Was obtained as white powdery crystals. The composition ratio of p-tert-butoxystyrene unit and p-methylstyrene unit in the obtained polymer was about 95: 5 from ¹ HNMR. Weight average molecular weight about 2000
0 (GPC method: polystyrene standard).

(2) Synthesis example 1 using 70 g of the poly (p-tert-butoxystyrene / p-methylstyrene) obtained in the above (1)
The reaction and post-treatment were carried out in the same manner as in (2) of 1, and the precipitated crystals were collected by filtration, washed with water, and dried under reduced pressure to obtain poly (p-methylstyrene / p-
47.6 g of hydroxystyrene) were obtained as white powdery crystals. The composition ratio of p-methylstyrene unit and p-hydroxystyrene unit in the obtained polymer was about 5:95 from ¹ HNMR.

(3) Using 15.0 g of the poly (p-methylstyrene / p-hydroxystyrene) obtained in the above (2) and 3.5 g of ethyl vinyl ether, the reaction and post-treatment were conducted in the same manner as in (3) of Synthesis Example 11. The precipitated crystals were collected by filtration, washed with water, and dried under reduced pressure to obtain 11.5 g of poly [p- (1-ethoxyethoxy) styrene / p-hydroxystyrene / p-methylstyrene] as white powder crystals. The composition ratio of p- (1-ethoxyethoxy) styrene unit to p-hydroxystyrene unit and p-methylstyrene unit in the obtained polymer was about 35: 60: 5 by ¹ HNMR.
Met. Weight average molecular weight: about 20000 (GPC method: polystyrene standard).

Synthesis Example 13 Synthesis of 1,3,5-tris (isopropoxymethoxy) benzene (1) Hydrogen chloride was introduced into a mixed solution of 95.1 g (2.38 mol) of 75% paraformaldehyde and 150.2 g (2.50 mol) of isopropanol, and the mixture was saturated. After stirring for 1 hour at room temperature, the mixture was allowed to stand and separated to separate an oily substance in the lower layer, which was dried over anhydrous calcium chloride. The desiccant was filtered off, and the filtrate was distilled under reduced pressure to obtain 190 g of isopropoxymethyl chloride of a bp. 36 to 39 ° C./80 mmHg fraction as a colorless oil. ¹ HNMR δ ppm (CDCl ₃ ): 1.16 to 1.24 (6H, d, CH ₃ ×)
2), 4.01~4.10 (1H, m , C H), 5.55 (2H, s, C H 2).

(2) 16.7 g (103.2 mmol) of phloroglucin was dissolved in 16.3 g (206.4 mmol) of pyridine, and 21.1 g (206.4 mmol) of acetic anhydride was added dropwise at 20 to 30 ° C.
The mixture was stirred and reacted at room temperature for 5 hours. After standing at room temperature overnight, the reaction solution was poured into 400 ml of water, extracted three times with ethyl acetate (100 ml), and the organic layer was washed with water (100 ml × 5) and then dried over anhydrous magnesium sulfate. The drying agent was separated by filtration and concentrated under reduced pressure to obtain 10.6 g of a residue mixture of acetyl compounds as a yellow oil. The obtained acetyl form was a mixture of a mono form and a di form by ¹ HNMR measurement.

(3) Sodium hydride (60%
5.65 g (0.14 mol) was suspended in 55 ml of toluene, and the acetylated mixture obtained in (2) above at 35 ° C. or lower was added thereto.
A solution of 10.6 g of N, N-dimethylformamide (25 ml) was added dropwise, and the mixture was stirred and reacted at room temperature for 2 hours. Next, 15.0 g (0.14 mol) of isopropoxymethyl chloride obtained in the above (1) was added dropwise at 25 ° C. or lower, and the mixture was stirred and reacted at room temperature for 3 hours.
After standing at room temperature overnight, the reaction solution was poured into 200 ml of ice water, extracted with methylene chloride (250 ml × 3), and the organic layer was washed with water (20 ml).
0 ml × 2) and dried over anhydrous magnesium sulfate. The drying agent is filtered off, concentrated under reduced pressure and the residual ether mixture 10.1
g were obtained as a brown oil. The resulting ether mixture is
^{From 1} HNMR measurement, it was a mixture of 1-isopropoxymethoxy-3,5-diacetylbenzene and 1-acetyl-3,5-diisopropoxymethoxybenzene.

(4) The ether mixture obtained in the above (3) 10.1
g and 30 g of anhydrous potassium carbonate were suspended in 120 ml of methanol, and reacted by stirring at room temperature for 7 hours. After standing at room temperature overnight, the reaction solution was poured into 100 ml of water, and ethyl acetate (100 ml) was added.
× 3) After extraction, the organic layer was washed with water (100 ml × 2) and dried over anhydrous magnesium sulfate. The drying agent was separated by filtration and concentrated under reduced pressure to obtain 10.2 g of a residual oily substance. This oil was separated by column chromatography [filler: Wakogel C-200;
Eluent: n-hexane / ethyl acetate = 1/1 (v / v)]
1,3-bis (isopropoxymethoxy) phenol 4.5g
Was obtained as a pale yellow oil.

(5) Under a nitrogen stream, sodium hydride (60%
0.2 g (5 mmol) was suspended in N, N-dimethylformamide (5 ml), and the 1,3-bis (isopropoxymethoxy) phenol obtained in (4) above at 25 ° C.
0 g (4.4 mmol) of N, N-dimethylformamide (10 m
l) The solution was added dropwise, and the mixture was stirred and reacted at room temperature for 2 hours. Then, isopropoxymethyl chloride obtained in the above (1) 3.6
g (33 mmol) was added dropwise at 25 ° C. or lower, and the mixture was stirred and reacted at room temperature for 3 hours. After standing overnight at room temperature, it was poured into 750 ml of water and extracted four times with 250 ml of ethyl acetate. 5% organic layer
4 times with 250 ml of sodium hydroxide aqueous solution, then 250 ml of water
And dried over anhydrous magnesium sulfate. The drying agent is filtered off, the filtrate is concentrated under reduced pressure, and the residue is separated by column chromatography [filler: Wakogel C-200 (Wako Pure Chemical Industries, Ltd., trade name); eluent: n-hexane / ethyl acetate =
10/1 → 5/1 → 3/1 (V / V)] to give 1.16 g of 1,3,5-tris (isopropoxymethoxy) benzene as a pale yellow oil. ¹ HNMR δppm (CDCl ₃ ): 1.15 to 1.20 (18H, d, CH ₃ ×)
6), 3.94 to 4.03 (3H, m, C H × 3), 5.28 (6H, s, C H ₂ ×
3), 6.41 (3H, s, aromatic ring).

Synthesis Example 14 Synthesis of 2,2-bis [4- (1-ethoxyethoxy) phenyl] propane 3,2-di (4-hydroxyphenyl) propane 32.0 g (0.1
4 mol) and 80.8 g (1.12 mol) of ethyl vinyl ether
Was dissolved in 130 ml of 1,4-dioxane, and 2.8 g of pyridinium p-toluenesulfonate was added, followed by stirring and reaction at 20 to 25 ° C. for 6 hours. After the reaction, 300 ml of ethyl ether and water
100 ml was injected, stirred at room temperature for 30 minutes, and allowed to stand. The organic layer was separated, washed with water (three times), dried over anhydrous magnesium sulfate, the solvent was distilled off, and 50.8 g of 2,2-bis [4- (1-ethoxyethoxy) phenyl] propane as a residue was slightly added. Obtained as a yellow oil. ¹ HNMR δ ppm (CDCl ₃ ): 1.18 to 1.24 (6H, t, CH ₃ CH ₂
× 2), 1.47 to 1.49 (6H, d, C H ₃ CH × 2), 1.63 (6H, s, C H
₃ × 2), 3.51 to 3.83 (4H, m, CH ₃ C H ₂ × 2), 5.31 to 5.37
(2H, m, C H × 2), 6.87~7.14 (8H, m, aromatic ring). IR (Neat) νcm ^-1 : 1610, 1580.

Synthesis Example 15 Synthesis of 2-cyclohexylcarbonyl-2- (p-toluenesulfonyl) propane (1) 23.9 g (0.98 g atom) of metallic magnesium (sharpened) was suspended in ethyl ether, and 160 g (0.98 g) of bromocyclohexane was stirred under reflux. Mol) and 1
The mixture was stirred and refluxed for hours. After cooling, the obtained Grignard reagent was added dropwise to a solution of 95 g (0.89 mol) of isobutyric acid chloride in ethyl ether at -5 to 0 ° C, and the mixture was stirred and reacted at the same temperature for 3 hours, and then left at room temperature overnight. The reaction solution was poured into water, the separated ether layer was separated, washed with water, and dried over anhydrous magnesium sulfate. After the desiccant was removed by filtration, the solvent was distilled off, and the residue was distilled under reduced pressure to obtain a bp. Of 95 to 100 ° C / 20 mmHg fraction.
50 g of 1-cyclohexyl-2-methyl-1-propanone was obtained as a pale yellow oil. _{^{1 HNMR δppm (CDCl 3):}} 1.06 (6H, d, C H 3 × 2), 1.1
2~1.87 (10H, m, cyclohexane ring hydrogen × 5), 2.51 (1H, m, cyclohexane ring C H), 2.76 (1H, m, C H). IR (Neat) vcm ^-1 : 1710.

(2) 1-cyclohexyl-2- obtained in the above (1)
42 g (0.31 mol) of sulfuryl chloride was added dropwise to 47.6 g (0.31 mol) of methyl-1-propanone at 25 to 35 ° C.
The mixture was stirred and reacted at 3.5 ° C. for 3.5 hours. The reaction solution was concentrated and distilled under reduced pressure to obtain 30.1 g of 2-chloro-1-cyclohexyl-2-methyl-1-propanone as a yellow oily substance at a bp of 99 to 105 ° C./18 mmHg fraction. ¹ HNMR δ ppm (CDCl ₃ ): 1.18 to 1.87 (16H, m, CH ₃ ×)
2, cyclohexane ring C H ₂ × 5), 3.13 (1H, m, cyclohexane ring C H ×
Five).

(3) 30.3 g (0.16 mol) of 2-chloro-1-cyclohexyl-2-methyl-1-propanone obtained in the above (2)
30.0 g (0.17 mol) of sodium p-toluenesulfinate was added to a dimethyl sulfoxide (DMSO) solution of
For 20 hours. The reaction solution was poured into cold water,
After stirring at ５5 ° C. for 1 hour, the precipitated crystals were collected by filtration, washed with water, and dried, and 18 g of crude crystals were recrystallized from a mixed solution of n-hexane / benzene to give 2-cyclohexylcarbonyl-2- (p-toluenesulfonyl). ) 13.5 g of propane were obtained as white needles. mp. 123-123.5 ° C. _{^{1 HNMR δppm (CDCl 3):}} 1.19~1.91 (16H, m, C H 3 × 2,
Cyclohexane ring × 5), 2.45 (3H, s, ArCH ₃ × 5), 3.25 (1
H, m, cyclohexane ring C H ), 7.33 (2H, d, J = 8Hz, aromatic ring 3-H, 5-
H), 7.65 (2H, d, J = 8 Hz, aromatic ring 2-H, 6-H). IR (KBr tablet) νcm ^-1 : 1705, 1310.

Synthesis Example 16 Synthesis of biscyclohexylsulfonyldiazomethane (1) 22.5 g (0.35 mol) of sodium azide was dissolved in a small amount of water and diluted with 130 ml of 90% aqueous ethanol. Then at 10-25 ° C p-toluenesulfonyl chloride
An ethanol solution in which 60 g (0.32 mol) was dissolved was added dropwise and reacted at room temperature for 2.5 hours. Then, the reaction solution was concentrated under reduced pressure, and the residual oily product was washed several times with water and dried over anhydrous magnesium sulfate. The drying agent was removed by filtration to obtain 50.7 g of p-toluenesulfonyl azide as a colorless oil. ¹ HNMR δ ppm (CDCl ₃ ): 2.43 (3H, s, C H ₃ ), 7.24
(2H, d, J = 8Hz, aromatic ring 3-H, 5-H), 7.67 (2H, d, J = 8Hz,
Aromatic ring 2-H, 6-H). IR (Neat) νcm ^-1 : 2120.

(2) Cyclohexanethiol 20.2 g (0.1
(7 mol), a solution of potassium hydroxide (12.0 g, 0.21 mol) in ethanol (50 ml) was added dropwise at room temperature, and the mixture was stirred and reacted at 30 ± 5 ° C. for 30 minutes. Then 18.2 g (2.14 mol) of methylene chloride
And stirred and reacted at 50 ± 5 ° C. for 6 hours. After standing overnight at room temperature, 55 ml of ethanol was poured into the reaction solution, diluted, 400 mg of sodium tungstate was added, and then 50 g (0.44 mol) of 30% hydrogen peroxide was added dropwise at 45 to 50 ° C, and further at the same temperature for 4 hours. The mixture was stirred and reacted. After the reaction, 200 ml of water was poured, and the mixture was allowed to stand at room temperature overnight. The precipitated crystals were collected by filtration, washed with water, and dried. Was. 137-139 ° C. ¹ HNMR δ ppm (CDCl ₃ ): 1.13 to 2.24 (20H, m, cyclohexane ring C H ₂ × 10), 3.52 to 3.66 (2H, m, cyclohexane ring C H ×
2), 4.39 (2H, s , C H 2). IR (KBr tablet) νcm ^-1 : 1320, 1305.

(3) 1.7 g of sodium hydroxide was dissolved in 70 ml of ethanol containing 60% water, and 12.1 g (0.04 mol) of biscyclohexylsulfonylmethane obtained in the above (2) was added thereto.
Was added. Then, a solution of 8.2 g (0.04 mol) of p-toluenesulfonyl azide obtained in the above (1) in ethanol (10 ml) was added dropwise at 5 to 10 ° C., and the mixture was stirred and reacted at room temperature for 7 hours. After standing at room temperature overnight, the precipitated crystals were collected by filtration, washed with ethanol, and dried to obtain 11 g of crude crystals, which were recrystallized from acetonitrile to obtain biscyclohexylsulfonyldiazomethane 8.0 g.
g were obtained as slightly yellow prism crystals. mp. 130-131 ° C. _{^{1 HNMR δppm (CDCl 3):}} 1.13~2.25 (20H, m, cyclohexane ring _{C H 2 × 10), 3.36~3.52} (2H, m, cyclohexane ring C H × 2
). IR (KBr tablet) νcm ^-1 : 2130, 1340, 1320.

Synthesis Example 17 Synthesis of bis (tert-butylsulfonyl) diazomethane (1) Synthesis Example 16 was prepared using 20.5 g (0.23 mol) of tert-butyl mercaptan instead of cyclohexanethiol.
The reaction and post-treatment were carried out in the same manner as in (2), and the obtained crude crystals were recrystallized from ethanol to obtain 9.3 g of bis (tert-butylsulfonyl) methane as white needles. mp.
152.5-155 ° C.

(2) Using 4.0 g (15.6 mmol) of bis (tert-butylsulfonyl) methane obtained in the above (1), the reaction and post-treatment were carried out in the same manner as in the synthesis example 16 (3). The resulting crude crystals were recrystallized from ethanol to obtain 2.4 g of bis (tert-butylsulfonyl) diazomethane as slightly yellow needles. mp. 121-121.5 ° C. ₁ H NMR δ ppm (CDCl ₃ ): 1.52 (18H, s, CH ₃ × 6). IR (KBr tablet) νcm ^-1 : 2120, 1330, 1315.

Synthesis Example 18 Synthesis of 9-anthrylpropyl acetate (1) 9.6 g (0.4 g atom) of metallic magnesium (sharpened) was suspended in tetrahydrofuran (50 ml), and 24 g (0.22 mol) of ethyl bromide was added dropwise under reflux with stirring. , 1
The mixture was stirred and refluxed for hours. Then 1-chloropropanol 24
g (0.25 mol) was added dropwise under reflux, and the mixture was stirred and refluxed for 1 hour. After cooling, the resulting Grignard reagent anthrone 1
9.4 g (0.1 mol) was added, and the mixture was stirred and refluxed for 4 hours. After cooling, a saturated aqueous ammonium chloride solution was poured into the reaction solution,
After extraction with ethyl ether, the ether layer was washed with water, dried over anhydrous magnesium sulfate, and concentrated. The residue obtained
Column chromatography separation of 22.4 g [filler: Wakogel C-200 (trade name of Wako Pure Chemical Industries, Ltd.); eluent: n-
Hexane / methylene chloride = 20/1 → 15/1 → 10/1 (V /
V)] to give 5.6 g of 9-anthracenepropanol as yellow crystals.

(2) Using 1.3 g (5.5 mmol) of 9-anthracenepropanol obtained in the above (1), the reaction and post-treatment were carried out in the same manner as in Synthesis Example 4 to obtain 2.1 g of crude orange crystals obtained.
Was recrystallized from n-hexane to give 9-anthrylpropyl acetate
0.9 g was obtained as pale yellow needles. mp. 107-109 ° C. _{^{1 HNMR δppm (CDCl 3):}} 2.24 (3H, s, C H 3 COO -), 2.2
_{4~2.30 (2H, m, -0CH 2} C H 2 CH 2), 3.78~3.84 (2H, t, Ar
-C H ₂ CH _2- ), 4.33 to 4.37 (2H, t, -OC H ₂ CH ₂ CH ₂ -A
r), 7.54 to 7.66 (4H, m, anthracene ring 2-H, 3-H, 6-H, 7
-H), 8.12 (2H, d, J = 9Hz, anthracene ring 4-H, 5-H),
8.36 (2H, d, J = 9 Hz, anthracene ring 1-H, 8-H), 8.46 (1
H, s, anthracene ring 10-H). IR (KBr tablet) νcm ^-1 : 1728. _{UV (CH 3 CN) ε (} λ = 248nm): 9.14 × 10 4.

Reference Example 5.0 g of each polymer obtained in Synthesis Example 7 to Synthesis Example 12 described above was mixed with propylene glycol monomethyl ether acetate 1
After dissolving in 5.0 g, passing through a 0.1 μm filter, spin-coating on a silicon wafer and heating at 90 ° C. for 90 seconds
A polymer film having a thickness of 1.0 μm was obtained. Then the developer (2.38
60% aqueous solution of tetramethylammonium hydroxide)
It was immersed in the paddle method for 2 seconds, and the solubility of the polymer film was observed. Table 1 shows the results.

[0131]

As apparent from Table 1, the polymers of (2) of Synthesis Example 7 and (2) of Synthesis Example 11 are resins soluble in an alkali developing solution. The polymer of Example 9, Synthesis Example 10, (3) of Synthesis Example 11 and (3) of Synthesis Example 12 is a resin which is hardly soluble in an alkali developing solution.

Example 1 A resist composition having the following composition was prepared, and a pattern was formed as described below. Poly [p- (1-ethoxyethoxy) styrene / p-hydroxystyrene] [Polymer of (3) of Synthesis Example 7] 5.0 g 2-cyclohexylcarbonyl-2- (p-toluenesulfonyl) propane [Acid of Synthesis Example 15] Generator] 0.3 g 9- (2-methoxyethoxy) methylanthracene [Far ultraviolet light absorber of Synthesis Example 1] 0.06 g Propylene glycol monomethyl ether acetate 14.7 g

A pattern forming method using the above resist composition will be described with reference to FIG. A resist composition 2 having the above composition is spin-coated on a high-reflectivity aluminum stepped substrate 1 obtained by performing photolithography, etching and aluminum sputtering on a silicon substrate.
After pre-baking on a hot plate at 90 ° C. for 90 seconds, a resist material film having a thickness of 1.0 μm was obtained (FIG. 1A). Then 248.4 nm
KrF excimer laser light (NA 0.50) 3 was selectively exposed through a mask 4 (FIG. 1B). And 100 ℃, 9
After post-baking on a hot plate for 0 seconds, development was performed for 60 seconds with an alkali developing solution (2.38% tetramethylammonium hydroxide aqueous solution) to dissolve and remove only the exposed portions of the resist material 2 to obtain a positive pattern 2a. (FIG. 1c). The obtained positive pattern had a resolution of 0.25 μm line and space, and had a good rectangular shape. The exposure amount at this time was 35 mJ / cm ² .

Example 2 A resist composition having the following composition was prepared. Poly (p-tert-butoxystyrene / p-hydroxystyrene) [Polymer of (2) of Synthesis Example 11] 4.5 g 2,2-bis [4- (ethoxyethoxy) phenyl] propane [Dissolution inhibiting compound of Synthesis Example 14] 1.5 g biscyclohexylsulfonyldiazomethane [acid generator of Synthesis Example 16] 0.3 g 9- (2-ethoxyethoxy) methylanthracene [far ultraviolet light absorber of Synthesis Example 2] 0.1 g 13.7 g of diethylene glycol dimethyl ether

Using the above resist composition, a pattern was formed in the same manner as in Example 1. As a result, 0.25μm
A positive pattern having line and space resolution was obtained, and the shape was rectangular and good. The exposure amount at this time was 38 mJ / cm ² .

Example 3 A resist composition having the following composition was prepared. Poly (p-vinylphenol) [Polymer of (2) of Synthesis Example 7] 4.5 g 1,3,5-Tris (isopropoxymethoxy) benzene [Crosslinkable compound of Synthesis Example 13] 1.8 g Bis (tert-butylsulfonyl) ) Diazomethane [Acid generator of Synthesis Example 17] 0.3 g 9- (2-methoxyethoxy) methylanthracene [Far ultraviolet light absorber of Synthesis Example 1] 0.07 g Ethyl lactate 13.4 g

Using the above resist composition, a pattern was formed in the same manner as in Example 1. As a result, 0.25μm
A negative pattern having line and space resolution was obtained, and the shape was rectangular and good. The exposure amount at this time was 36 mJ / cm ² .

Embodiments 4 to 11 Resist compositions having the compositions shown in Tables 2 and 3 below were respectively prepared.

[0140]

Using each of the resist compositions prepared as described above, a pattern was formed in the same manner as in Example 1. Table 4 shows the results.

[0142]

Comparative Example 1 A resist composition having the following composition was prepared by removing the far ultraviolet light absorber according to the present invention from the resist composition of Example 1. Poly [p- (1-ethoxyethoxy) styrene / p-hydroxystyrene] 5.0 g 2-cyclohexylcarbonyl-2- (p-toluenesulfonyl) propane 0.3 g Propylene glycol monomethyl ether acetate 14.7 g

Using the above resist composition, a pattern was formed in the same manner as in Example 1. As a result, the lower layer of the unexposed portion was partially dissolved by the influence of halation, and the positive pattern 2′a was extremely poor (FIG. 2). Such a defective pattern leads to a defect in a subsequent process and is unusable.

Comparative Examples 2-5. Resist compositions having the compositions shown in Table 5 below were prepared by removing the far ultraviolet light absorber according to the present invention from the resist compositions of Examples 1, 2, 5, and 7, respectively.

[0146]

Example 1 using each of the resist compositions shown in Table 5
A pattern was formed in the same manner as described above. As a result, in each case, the lower layer of the unexposed portion was partially dissolved under the influence of halation, and the pattern was extremely poor as in Comparative Example 1.
Such a defective pattern leads to a defect in a subsequent process, and is unusable.

[0148]

As is apparent from the above description, the resist composition of the present invention can be used as a resist material for exposure to far ultraviolet light (300 nm or less) or KrF excimer laser light (248.4 nm) or the like. When used for highly reflective substrates or stepped substrates such as aluminum-silicon, aluminum-silicon-copper, or tungsten silicide, notching or halation that causes problems such as disconnection while maintaining high resolution performance and high sensitivity. And a good pattern shape of quarter micron can be obtained without generation of cracks. Therefore, the present invention has great value for forming ultrafine patterns in the semiconductor industry and the like. The resist composition of the present invention is particularly effective for pattern formation using deep ultraviolet light or KrF excimer laser light, but can be sufficiently used for pattern formation using electron beams, X-rays and the like. is there.

[0149]

[Brief description of the drawings]

FIG. 1 is a cross-sectional view of a positive pattern on a highly reflective substrate using a resist composition of the present invention.

FIG. 2 is a cross-sectional view of a pattern formation defect observed when an attempt was made to form a positive pattern on a highly reflective substrate using the resist composition of the comparative example.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... Aluminum step board, 2 ... The resist material concerning this invention, 3 ... KrF excimer laser light, 4 ... Mask,
2a: resist pattern, 2'a: resist pattern.

──────────────────────────────────────────────────の Continued on the front page (72) Inventor Akiko Katsuyama 1006 Kazuma Kadoma, Osaka Prefecture Inside Matsushita Electric Industrial Co., Ltd. (72) Kazuhiro Yamashita 1006 Kazama Kadoma Kadoma City, Osaka Matsushita Electric Industrial Co., Ltd. In-house (56) References JP-A-3-237106 (JP, A) JP-A-1-307740 (JP, A) JP-A-3-200257 (JP, A) JP-A-5-181265 (JP, A) JP-A-7-316268 (JP, A) JP-A-7-84364 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) G03F ^7/ 00-7/18

Claims (6)

(57) [Claims] (1) The following (i) to (iii) (i) a resin which becomes alkali-soluble by removing a protecting group by the action of an acid, and (ii) a resin which becomes free of an alkali-soluble resin by the action of an acid. And (iii) a combination of an alkali-soluble resin and a compound that cross-links with the resin by the action of an acid to make the resin hardly alkali-soluble. Compound and the following general formula [1] [Wherein, R ¹ is an alkyl group having 1 to 6 carbon atoms, a general formula [2] (Wherein, R ² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ³ represents an alkyl group having 1 to 6 carbon atoms,
Represents an integer of 0 to 3. Or a group represented by the general formula [3]: (In the formula, R ⁴ represents an alkyl group having 1 to 6 carbon atoms, a phenyl group or a substituted phenyl group.)
Represents an integer of 1 to 5. ] The resist composition characterized by comprising the anthracene derivative shown by these, and a solvent. 2. A resin which becomes alkali-soluble by removing a protecting group by the action of an acid is represented by the following general formula [4]: [Wherein, R ⁵ and R ⁸ each independently represent a hydrogen atom or a methyl group, and R ⁶ represents a tert-butoxycarbonyl group, a tert-butyl group, a tert-butoxycarbonylmethyl group, a 1-methylcyclohexyloxycarbonylmethyl Group, tetrahydropyranyl group, 2-vinyloxyethyl group, vinyloxymethyl group, acetyl group, or the general formula [5] (Wherein, R ¹⁰ represents a hydrogen atom or a methyl group; R ¹¹ represents a linear or branched alkyl group having 1 to 3 carbon atoms;
¹² represents a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms. Wherein R ⁷ is a hydrogen atom, a cyano group or a general formula [6] (Wherein, R ¹³ is a hydrogen atom, a halogen atom, a carbon number of 1 to 6)
Represents a linear or branched alkyl group, a linear or branched alkoxy group having 1 to 6 carbon atoms, a tert-butoxycarbonyloxy group, or an acetyloxy group. R ⁹ represents a hydrogen atom, a cyano group, or —COO
Y (where Y represents a linear or branched alkyl group having 1 to 6 carbon atoms), k and t each independently represent a natural number, and j represents 0 or a natural number (however, 0.2 <(K + j)
/(K+t+j)<0.8, and when j is a natural number, 0.05 ≦ j / (k + t + j) ≦ 0.50. ). The resist composition according to claim 1, which is a polymer represented by the formula: 3. A resin which becomes alkali-soluble by removing a protecting group by the action of an acid, wherein R ⁵ ,
R ⁸ and R ⁹ are hydrogen atoms, and R ⁶ is a group represented by the above general formula [5]
(Wherein, R ¹⁰ , R ¹¹ and R ¹² are the same as defined above), and R ⁷ is a group represented by the general formula [6] (wherein, R ¹³ is the same as defined above). The resist composition according to claim 2, wherein the polymer is: 4. An alkali-soluble resin represented by the following general formula [7]: Wherein, R ¹⁴ represents a hydrogen atom or a methyl group, R ¹⁵ is te
rt-butoxycarbonyl group, tert-butoxycarbonylmethyl group, tert-butyl group, tetrahydropyranyl group, acetyl group, or the general formula [5] (Wherein, R ¹⁰ , R ¹¹ and R ¹² are the same as defined above), and R ¹⁶ is a hydrogen atom, a halogen atom, or a linear or branched alkyl having 1 to 6 carbon atoms. Represents a group, r represents a natural number, p and q each independently represent 0 or a natural number (provided that 0 ≦ (p + q) / (r + p + q) ≦ 0.2). The resist composition according to claim 1, which is a polymer represented by the formula: 5. An alkali-soluble resin having the general formula [7]:
In the formula, R ¹⁴ is a hydrogen atom, and R ¹⁵ is a tert-butyl group, an acetyl group, or the above general formula [5] (wherein R ¹⁰ ,
R ¹¹ and R ¹² are the same as above. 5. The resist composition according to claim 4, which is a polymer which is a group represented by the formula: 6. A step of (i) applying the resist composition according to claim 1 on a semiconductor substrate or the like, and then heating; (ii)
(Ii) exposing with deep ultraviolet light or KrF excimer laser light through a mask, and then, if necessary, performing a heat treatment;
i) a step of developing with an alkaline developer. [0001]