JPH07319155A - Resist composition for far ultraviolt ray and fine pattern forming method using the same - Google Patents

Abstract

PURPOSE:To obtain this resist compsn. capable of inhibiting halation and notching while maintaining high resolution and high sensitivity by incorporating a photosensitive compd. which generates an acid by exposure, a specified anthracene deriv. and a solvent and to provide a fine pattern forming method using the same resist compsn. CONSTITUTION:This resist compsn. contains a combination of a resin which releases protective groups by the action of an acid and becomes alkali-soluble or an alkali-soluble resin wifh a compd. which releases a protective group by the action of the acid and becomes alkali-soluble or a combination of an alkali-soluble resin with a compd. which crosslinks the resin by the action of an acid and makes the resin slightly alkali-soluble, a photosensitive compd. which generates an acid by exposure, an anthracene deriv. or groups represented by formulae I to III III (where R<1> R<3> and R<4> are 1-6C alkyl R2 is H or 1-4C alkyl. (n) is an integer of 1-5 and (m) is an integer of 0-3) and a solvent.

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 IC and LSI, and a fine pattern forming method using the same. For more information,
Far ultraviolet light of 300 nm or less or KrF as an exposure energy source
A chemically amplified positive (or negative) resist composition that is particularly effective when forming a fine pattern on a high-reflectance substrate such as aluminum, polysilicon, aluminum-silicon, or tungsten silicide using excimer laser light (248.4 nm) The present invention relates to an object and a method for forming a fine pattern using the object.

[0002]

2. Description of the Related Art In recent years, with the high integration of semiconductor devices, exposure equipment used for microfabrication, especially photolithography, has become shorter and shorter in wavelength. At present, KrF excimer laser light (248.4 nm) and far-ultraviolet light are used. Utilization has been studied, and many chemically amplified resist materials usable for this light source have been reported. When a high density integrated circuit is manufactured using these light sources, a chemically amplified resist material is used to form a fine pattern on various substrates. Highly reflective substrates such as aluminum, polysilicon, aluminum-silicon, and tungsten silicide are used. In the above, in a normal chemically amplified resist material, a photosensitivity phenomenon of an unnecessary area occurs due to the reflection of light on the substrate surface or the 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), which has a shorter wavelength than conventional g-line (436 nm) and 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 absorbing agent or a bleaching agent like a resist for g-rays and a resist for i-rays. However, when a light absorbing agent is used, the light transmittance is lowered, and as a result, The resolution performance becomes poor. Further, for example Jiazojiketo group in the molecule _{[-COC (= N 2) CO-} ] and diazoketo group [-CO
When a bleaching agent having C (= N ₂ )-] is used, the sensitivity is extremely lowered, so that neither can be used. On the other hand, EPC Publication No. 543762, phenoxymethylanthracene, anthracenemethanol, 9, as a far ultraviolet absorber.
10-diphenylanthracene and the like are disclosed. However, these anthracene derivatives have poor solubility in a resist solvent, and even if they are dissolved, they have problems such as precipitation during storage and causing particles, so that they are not suitable for resist compositions. It cannot be used as a UV absorber. Therefore, there is a strong demand for the emergence of a practical chemically amplified positive (or negative) resist composition capable of preventing halation and the like in such a short wavelength region.

[0003]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned circumstances, and provides a far-ultraviolet light, a KrF excimer laser light, etc. on a highly reflective substrate having steps such as aluminum, polysilicon, aluminum-silicon, and 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 fine pattern forming method using the same.

[0004]

To achieve the above object, the present invention comprises the following configurations. "(1) The following (i) to (iii) (i) a resin that becomes alkali-soluble by removing a protective group by the action of an acid, (ii) an alkali-soluble resin and a resin that becomes an alkali-soluble by the action of an acid. Any one of a combination with a compound that becomes alkali-soluble, (iii) a combination of an alkali-soluble resin and a compound that crosslinks with the resin by the action of an acid to make the resin insoluble in an alkali, and a photosensitivity that generates an acid by exposure. Compound and the following general formula [1]

[0005]

[Chemical 9]

[In the formula, R ¹ is an alkyl group having 1 to 6 carbon atoms;

[0007]

[Chemical 10]

(In the formula, R ² is a hydrogen atom or a carbon number of 1 to 4
Represents an alkyl group, 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]

[Chemical 11]

(In the formula, 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 including the anthracene derivative shown by these, and a solvent.

(2) (i) The above (1) is formed on a semiconductor substrate or the like.
After applying the resist composition according to, the step of heating, (ii) the step of exposing with deep ultraviolet light or KrF excimer laser light through a mask, and then subjecting to heat treatment, and (iii) an alkali A method for forming a fine pattern, which comprises a step of developing with a developing solution. ]

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

[0013]

[Chemical 12]

A chemical amplification resist composition containing a compound represented by the formula (wherein R ¹ and n are the same as above) as a far-ultraviolet light absorber for preventing halation and notching can achieve the object. Heading out, the present invention has been completed.

In the above general formula [1], R ¹ has ¹ carbon atom.
~ 6 alkyl group, a group represented by the general formula [2] or a group represented by the general formula [3], the alkyl group having 1 to 6 carbon atoms, a methyl group, an ethyl group, a propyl group, butyl Examples thereof include groups, amyl groups and hexyl groups (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 has 1 carbon atom.
Represents an alkyl group of 6 to 6, but has 1 to 6 carbon atoms represented by R ² .
The alkyl group of 4 is a methyl group, an ethyl group, a propyl group, or 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 (in any of linear, branched, and cyclic groups. May be used).

In the general formula [3], R ⁴ has 1 carbon atom.
~ 6 represents an alkyl group, a phenyl group or a substituted phenyl group.
Examples thereof 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 examples of the substituent of the substituted phenyl group include 1 to 1 carbon atoms. Examples thereof include an alkyl group having 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a halogen atom.

As the resin used in the present invention, which becomes alkali-soluble by removing the protecting group by the action of acid, for example, the following general formula [4]

[0019]

[Chemical 13]

[In the formula, R ⁵ and R ⁸ each independently represent a hydrogen atom or a methyl group, and R ⁶ is a tert-butoxycarbonyl group, a tert-butyl group, a tert-butoxycarbonylmethyl group, or 1-methylcyclohexyl. Oxycarbonylmethyl group, tetrahydropyranyl group, 2-vinyloxyethyl group, vinyloxymethyl group, acetyl group, or general formula [5]

[0021]

[Chemical 14]

(In the formula, 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 direct alkyl group having 1 to 6 carbon atoms. Represents a chain, branched or cyclic alkyl group), and R ⁷ represents a hydrogen atom, a cyano group or a general formula [6].

[0023]

[Chemical 15]

(In the formula, 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 (wherein Y represents a linear or branched alkyl group having 1 to 6 carbon atoms), k and t independently represents a natural number, 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. ) Represents. ] The polymer shown by these is mentioned. Specific examples thereof include poly (p-tert-butoxystyrene / p-hydroxystyrene), poly (p-tert-butoxycarbonyloxystyrene / p-hydroxystyrene), poly (p-tetrahydropyranyloxystyrene /
p-hydroxystyrene), 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-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 (p-vinylphenoxyacetate 1-methylcyclohexyl / p-hydroxystyrene), poly (p-vinylphenoxyacetate tert-butyl / p-hydroxystyrene), poly (p-vinylphenoxyacetate tert-butyl / p -
Hydroxystyrene / methyl methacrylate) and the like.

Among the polymers represented by the general formula [4], particularly preferable ones are those in which R ⁵ , R ⁸ and R ⁹ are hydrogen atoms,
R ⁶ is a group represented by the above general formula [5] (in the formula, R ¹⁰ , R ¹¹ and R ¹² are the same as the above), and R ⁷ is the above general formula [6] (in the formula, R ¹³ is The same as the above), which is a group of polymers. Specific examples of these preferable 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 (p-vinylphenoxyacetic acid 1-methylcyclohexyl / p-hydroxystyrene), poly (p-vinylphenoxyacetic acid tert-butyl / p-
(Hydroxystyrene) and the like.

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

[0027]

[Chemical 16]

[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 general formula. [5]

[0029]

[Chemical 17]

(Wherein R ¹⁰ , R ¹¹ and R ¹² are the same as defined above), 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 of the formula, r represents a natural number, and p and q are each independently 0 or a natural number (where 0 ≦ (p + q) / (r + p + q)
≦ 0.2. ) Represents. ] 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) [However, 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 unit to p-hydroxystyrene unit is 2
↓: Limited to 8 ↑. ], Poly (p-vinylphenoxyacetate tert-butyl / p-hydroxystyrene) [however,
The ratio of tert-butyl p-vinylphenoxyacetate units to p-hydroxystyrene units is limited to 2 ↓: 8 ↑. ], Poly (p-1-ethoxyethoxystyrene / p-tert
-Butoxystyrene / p-hydroxystyrene) [however,
The ratio of p-1-ethoxyethoxystyrene units and p-tert-butoxystyrene units to p-hydroxystyrene units is limited to 2 ↓: 8 ↑. ], Poly (p-tert-butoxystyrene / styrene / p-hydroxystyrene) [however,
p-tert-butoxystyrene unit and styrene unit, p-
The ratio of hydroxystyrene units is limited to 2 ↓: 8 ↑. ] Etc. are mentioned.

Among the polymers represented by the general formula [7], 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) [however, the ratio of p-tert-butoxystyrene unit to p-hydroxystyrene unit is Is limited to 2 ↓: 8 ↑. ], Poly (p-1-ethoxyethoxystyrene / p-hydroxystyrene) [However, the ratio of p-1-ethoxyethoxystyrene unit to p-hydroxystyrene unit is 2 ↓: 8 ↑
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 ↑. ] Etc. are mentioned.

A compound used in the present invention, which becomes alkaline soluble by removing a protecting group by the action of an acid (hereinafter, referred to as
It is abbreviated as "lysis inhibitor compound". ) Is the following general formula [8]

[0034]

[Chemical 18]

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

[0036]

[Chemical 19]

(In the formula, R ¹⁰ , R ¹¹ and R ¹² are the same as defined above). ] The compound shown by the following general formula [9]

[0038]

[Chemical 20]

[In the formula, R ¹⁷ is the same as above. ] The compound shown by these, or various acetal compounds are mentioned. 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,
Examples thereof include O-acetal, propionaldehyde acetal, propionaldehyde N, O-acetal, butyraldehyde acetal, butyraldehyde N, O-acetal.

The compound 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]

[Chemical 21]

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

[0043]

[Chemical formula 22]

(Wherein R ¹⁸ is the same as defined above). ] The compound shown by these, or the following general formula [1
2]

[0045]

[Chemical formula 23]

[In the formula, R ²⁰ is a hydrogen atom, or 1 to 10 carbon atoms.
6 represents a linear, branched or cyclic alkyl group represented by R ²¹
Is a hydrogen atom or the general formula [13]

[0047]

[Chemical formula 24]

(Wherein R ²⁰ is the same as defined above). ] The compound etc. which are shown are mentioned. Specific examples of these crosslinkable compounds include 1,2,4-tris (cyclohexyloxymethoxy) benzene, 1,2,4-tris (isobutoxymethoxy) benzene, 1,2,4-tris (isopropoxymethoxy) benzene. ) 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 can be mentioned.

The photosensitive compound capable of generating an acid upon exposure (hereinafter abbreviated as "acid generator") used in the present invention is literally a photosensitive compound capable of generating an acid upon exposure to form a resist pattern. Any of them may be used as long as they do not adversely affect the above formula. Particularly preferred in the present invention are the following general formula [14] and general formula [1
5], general formula [16], general formula [17] and general formula [1
8] or a combination of these compounds.

[0050]

[Chemical 25]

[In the formula, R ²² and R ²³ each independently represent a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, a phenyl group or a substituted phenyl group, and R ²⁴ represents a carbon atom. Number 1
3 represents a linear or branched alkyl group. ]

[0052]

[Chemical formula 26]

[In the formula, 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]

[Chemical 27]

[Wherein R ²⁷ and R ²⁸ each independently represent a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, a phenyl group or a substituted phenyl group, and A is a sulfonyl group. Alternatively, it represents a carbonyl group. ]

[0056]

[Chemical 28]

[In the formula, 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 1 carbon atoms. 8 represents a perfluoroalkyl group. ]

[0058]

[Chemical 29]

[In the formula, 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, a methane group. It represents a sulfonyl group or a trifluoromethanesulfonyl group. ]

Specific examples of the acid generator used in the present invention include 2-methanesulfonyl-2-methyl- (4-methylthio) propiophenone and 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 can be mentioned.

The resin according to the present invention, which is alkali-soluble by removing the protecting group by the action of an acid, is disclosed in, for example, JP-A-4-1122.
58 (US Pat. No. 5,350,660), Japanese Patent Laid-Open No. 4-25
It can be easily obtained by the method described in 1259 (EPC Publication No. 476865).

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

The compound of the present invention, which is alkali-soluble by removing a protecting group by the action of an acid, is described in, for example, JP-A-4-88.
It can be easily obtained by the method described in Japanese Patent No. 348, etc.

The acid generator according to the present invention is disclosed in, for example, JP-A-4-
211258 (US Pat. No. 5,350,660), JP
It can be easily obtained by the method described in 4-251259 (EPC Publication No. 476865), JP-A-4-210960 (US Pat. No. 5216135), and the like.

As the solvent used in the present invention, any of the above (i) to (iii), an acid generator capable of generating an acid upon exposure, and a compound represented by the general formula [1] can be dissolved. Any material may be used, but a material having a good film-forming property is usually 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,
4-dioxane, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, ethylene glycol isopropyl ether and the like can be mentioned, but they are not limited to these.

Specific examples of the compound represented by the general formula [1] used as a far-ultraviolet light absorber in the present invention (hereinafter sometimes abbreviated as "far-ultraviolet light absorber" according to the present invention). As an example, 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} anthracene, 9-methoxymethylanthracene, 9-ethoxymethylanthracene, 9-isopropoxymethylanthracene, 9-methoxymethoxymethylanthracene, acetic acid 9-anthrylmethyl, propionate 9-anthrylmethyl, p- Examples include 9-anthrylmethyl methylbenzoate, 9-anthrylmethyl benzoate, 9-anthrylpropyl acetate and the like.

The compound represented by the general formula [1], which is used as a far ultraviolet light absorber in the present invention, is, for example,
It can be easily synthesized by the ~ C method.

(Method A) The following general formula [19]

[0069]

[Chemical 30]

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

[0071]

[Chemical 31]

(Wherein R ¹ is the same as above) 0.5 to 100 times mol of benzene, in the presence of acids such as sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid or p-toluenesulfonic acid, benzene, The reaction is carried out in an organic solvent such as toluene or cyclohexane with or without a solvent at 20 to 150 ° C., preferably 50 to 130 ° C. for 0.5 to 10 hours with stirring and post-treatment according to a conventional method to give the desired general formula [1]. The compound is easily obtained.

(Method B) 1 mol of the compound represented by the above general formula [19] and a halogenating agent (eg, thionyl chloride,
Phosphorus oxychloride, phosphorus trichloride, phosphorus pentachloride, sulfuryl chloride,
Hydrogen chloride, hydrochloric acid, phosphorus oxybromide, phosphorus tribromide, phosphorus pentabromide,
Examples thereof include hydrogen bromide, hydrobromic acid, hydrogen iodide and the like. )
1 to 10 times mol is reacted with stirring 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]

[Chemical 32]

An alkyl chloride compound represented by the formula (wherein n is the same as above) is obtained.

Then, 1 mol of the alkyl chloride compound represented by the above general formula [22] and 0.5 to 100 times mol of the compound represented by the above general formula [20] are mixed with or without a catalyst (for example, sodium hydroxide or water). Potassium oxide, tert-
Examples include butoxy potassium, sodium, potassium, sodium methoxide, sodium ethoxide, sodium hydride and the like. ) In the presence of a suitable solvent (methylene chloride, benzene, toluene, n-hexane, xylene, tetrahydrofuran, etc.) at 20-150 ℃ 0.5.
The desired compound represented by the general formula [1] can be easily obtained by stirring the reaction for 20 hours and subjecting the reaction solution to post-treatment according to a conventional method.

(Method C) 1 mol of the compound represented by the above general formula [20] and a halogenating agent (eg, thionyl chloride,
Phosphorus oxychloride, phosphorus trichloride, phosphorus pentachloride, sulfuryl chloride,
Hydrogen chloride, hydrochloric acid, phosphorus oxybromide, phosphorus tribromide, phosphorus pentabromide,
Examples thereof include hydrogen bromide, hydrobromic acid, hydrogen iodide and the like. )
1 to 10 times mol is reacted with stirring 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 the reaction solution is subjected to a conventional method. The post-treatment according to the following general formula [2
2]

[0078]

[Chemical 33]

(Wherein, X represents a halogen atom and R ¹ is the same as the above), and a compound represented by the formula is obtained.

Next, 1 mol of the compound represented by the general formula [22] and compounds 1 to 1 represented by the general formula [19].
20 times mol and a base (for example, sodium hydroxide, potassium hydroxide, sodium hydride, sodium methoxide, sodium ethoxide, potassium tert-butoxide,
Examples include triethylamine, diethylamine, pyridine, piperidine and the like. ) In the presence of a suitable solvent (methylene chloride, benzene, toluene, xylene, tetrahydrofuran, 1,4-dioxane, etc.) in 20 to 15
The desired compound represented by the general formula [1] can be easily obtained by subjecting the reaction mixture to stirring reaction at 0 ° C. for 0.5 to 10 hours and post-treating the reaction solution according to a conventional method.

The resist material of the present invention is usually composed of the above-mentioned 4 components (resin which becomes alkali-soluble by the action of acid, acid generator, far-ultraviolet light absorber and solvent), or 5 components (alkali-soluble resin, dissolution). An inhibitor compound, an acid generator, a far-ultraviolet light absorber and a solvent, or an alkali-soluble resin, a crosslinkable compound, an acid generator, a far-ultraviolet light absorber and a solvent) are the main components, but if necessary, In addition to these, sensitivity adjusting agents [eg, basic resins such as polyvinyl pyridine, poly (vinyl pyridine / methyl methacrylate), poly (vinyl pyridine / p-methyl styrene), and pyridine, piperidine, triethylamine, diethylamine, tetramethyl, etc. Examples thereof include organic base compounds such as ammonium hydroxide. ], A plasticizer [eg, diethyl phthalate, dibutyl phthalate, dipropyl phthalate and the like. ], And one or more kinds of surfactants (for example, nonionic or fluorine-containing nonionic surfactants, etc.) may be appropriately added.

In the resist composition of the present invention, the mixing ratio of the resin, which becomes alkali-soluble by removing the protective group by the action of an acid, and the acid generator is 100 parts by weight of the resin. The amount is usually 1 to 30 parts by weight, preferably 1 to 20 parts by weight.

In the resist composition of the present invention, the mixing ratio of the alkali-soluble resin and the dissolution inhibiting compound is
The dissolution inhibiting compound is usually 10 to 50 parts by weight, preferably about 15 to 40 parts by weight with respect to 100 parts by weight, and as a mixing ratio of the alkali-soluble resin and the dissolution inhibiting compound and the acid generator, an alkali is used. The acid generator is usually 1 per 100 parts by weight of the total of the soluble resin and the dissolution inhibiting compound.
-30 parts by weight, preferably 1-20 parts by weight.

In the resist composition of the present invention, the mixing ratio of the alkali-soluble resin and the crosslinking compound is usually 10 to 50 parts by weight based on 100 parts by weight of the resin.
Parts by weight, preferably 15 to 40 parts by weight and the like, further alkali-soluble resin and a crosslinkable compound, as a mixing ratio of the acid generator, a total of alkali-soluble resin and a crosslinkable compound 100 parts by weight Whereas the acid generator is usually 1
-30 parts by weight, preferably 1-20 parts by weight.

As the amount of the solvent in the resist composition of the present invention, the above-mentioned three compositions [(i) + acid generator, (i
i) + acid generator, and (iii) + acid generator], and each composition is prepared by adding at least one far-ultraviolet light absorber (compound represented by the general formula [1]) according to the present invention. As a result, the amount of the resist composition obtained is not particularly limited as long as it does not hinder the application of the resist composition on the substrate, but usually the protective group is eliminated by the action of an acid to become alkali-soluble. Resin, or the total of the alkali-soluble resin and the dissolution inhibiting compound, or the total of the alkali-soluble resin and the crosslinkable compound, 100 to 2000 parts by weight for each 100 parts by weight,
It is preferably 150 to 600 parts by weight.

Further, the addition amount of the far-ultraviolet light absorber according to the present invention is 0.05 to 0.05 with respect to the resin of various resist constituent components.
20% by weight, preferably 0.1 to 10% by weight.

Further, the developing solution used in the above-mentioned various pattern forming methods is suitable for increasing the difference in dissolution rate between the exposed and unexposed areas depending on the solubility of the resist composition. It suffices to select an alkaline solution having a concentration, which is usually selected from the range of 0.01 to 20%. Examples of the alkaline solution used include tetramethylammonium hydroxide (TMAH), choline, organic amines such as triethanolamine, and solutions containing inorganic alkalis such as NaOH and KOH. It is particularly preferable that the resist composition of (1) is developed using an existing aqueous solution of TMAH.

Pattern formation using the resist composition of the present invention may be carried out as follows, for example.

A resist composition containing a far-ultraviolet light absorber according to the present invention is coated on a highly reflective substrate such as aluminum to a thickness of about 0.5 to 2 μm (0.1 when used as an upper layer of three layers). .About.0.5 .mu.m), and pre-bake this in an oven at 70 to 130.degree. C. for 10 to 30 minutes or on a hot plate at 70 to 130.degree. C. for 1 to 2 minutes. Next, hold a mask for forming the desired pattern over the resist film and irradiate it with far-ultraviolet light of 300 nm or less or KrF excimer laser light (248.4 nm) so that the exposure amount is about 1 to 100 mJ / cm ^2. After that, if necessary, bake on a hot plate at 70 to 150 ° C. for 1 to 2 minutes. Furthermore 0.1 ~
5% tetramethylammonium hydroxide (TMAH)
Using a developer such as an aqueous solution, soak (di
By developing by a conventional method such as the p) method, the puddle method, or the spray method, the desired positive or negative pattern is formed on the substrate with a good shape.

[0090]

[Operation] When a resist film obtained by applying the resist composition according to the present invention onto a highly reflective substrate of aluminum, polysilicon, aluminum-silicon, tungsten silicide or the like is irradiated with far ultraviolet light, the exposed portion is exposed to far 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, optical interference in the resist film is reduced. Further, the reflected light to the unexposed portion is easily absorbed. Therefore, the influence of halation and standing waves is reduced.

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

Further, the far-ultraviolet light absorber used in the resist composition according to the present invention has been conventionally suggested to have a decrease in absorbance upon irradiation with far-ultraviolet light, and a diazoketo group, a diazodiketo group in the molecule, When compared with a photosensitive compound having a diazodisulfonyl group or a diazoketosulfonyl group, these compounds have the drawbacks that they have a large decrease in sensitivity, and because the light absorption intensity near 250 nm is small, a large amount of Necessitates addition, resulting in pattern shape,
Since it completely overcomes the drawbacks such as poor resolution performance, it has a high reflection that could not be achieved sufficiently by using conventional compounds of this kind, and good pattern formation even on a substrate with steps. Made possible.

Further, since the far-ultraviolet light absorber used in the resist composition according to the present invention has a very good solubility in a solvent, the existing anthracene derivative was used even when the resist composition was stored for a long period of time. There is no precipitate as seen in some cases, and it is 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 thereto.

[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 2-methoxyethanol (450 ml) was injected under reflux to give 1.5.
The mixture was stirred and refluxed for hours. After leaving it at room temperature overnight, it was washed with a saturated aqueous solution of sodium hydrogencarbonate, dried over anhydrous magnesium sulfate, and 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 δ ppm (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) ν cm ^-1 : 1130. UV (CH ₃ CN) ε (λ = 248nm): 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 thionyl chloride 32.3
Inject benzene (300ml) solution of g (0.27mol),
The mixture was stirred and refluxed for hours. Pour the reaction solution 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 the desiccant was filtered off, the solvent was distilled off to obtain 51.2 g of a crude residue of 9-chloromethylanthracene as an orange-yellow oily substance.

(2) The crude 9-chloromethylanthracene (5.2 g, 23 mmol) obtained in the above (1) and 300 ml of 2-ethoxyethanol were reacted with stirring at room temperature for 10 hours, and the reaction solution was mixed with water.
It 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, the solvent was distilled off, and the crude oily substance obtained as a residue was 2.75 g.
Column chromatography separation [filler: Wakogel 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, C H ₃ CH ₂
O), 3.49 ~ 3.57 (2H, q, CH ₃ C H ₂ O), 3.59 ~ 3.63 (2H, t,
-OCH ₂ C H ₂ O-CH ₂ CH ₃ ), 3.76-3.80 (2H, t, -OC H ₂ CH ₂
-OCH ₂ CH ₃ ), 5.56 (2H, s, Ar-C H ₂ O-), 7.46 ~ 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 = 248nm): 8.34 × 10 ⁴ .

Synthesis Example 3. Synthesis of 9-ethoxymethylanthracene Crude 9-chloromethylanthracene obtained in (1) of Synthesis Example 2
After 5.2 g (23 mmol) and 700 ml of ethanol were stirred and reacted at room temperature for 10 hours, the reaction mixture 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 crude crystals obtained as a residue were recrystallized from a 50% aqueous tetrahydrofuran solution 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, C H ₃ CH ₂
O-), 3.73 to 3.75 (2H, q, CH ₃ C H ₂ O-), 5.46 (2H, s, A
rC H ₂ O-), 7.45 to 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) ν cm ^-1 : 1092. UV (CH ₃ CN) ε (λ = 248nm): 8.09 × 10 ⁴ .

Synthesis Example 4. Synthesis of 9-anthrylmethyl acetate 9-anthracene Methanol 15.0 g (72 mmol) triethylamine 7.3 g (72 mmol) methylene chloride 1
It was dissolved in 00 ml and 120 ml of 1,4-dioxane and cooled. Then acetyl chloride 6.8 g (86.4 mmol) 5
The mixture was added dropwise at 10 ° C, and the mixture was reacted at the same temperature for 2.5 hours with stirring. After the reaction, the reaction solution was poured into 350 ml of ice water, acidified with 10% hydrochloric acid aqueous solution, and extracted with 100 ml of methylene chloride. The separated organic layer was washed with 100 ml of water once and saturated aqueous sodium hydrogen carbonate solution.
After washing once with 100 ml, it was washed once with 100 ml of water and dried over anhydrous sodium sulfate. The desiccant was filtered off and the solvent was distilled off to obtain 17.7 g of crude crystals which were recrystallized from n-hexane to obtain acetic acid 9-
Anthrylmethyl 11.0 g was obtained as yellow needle crystals. m
p. 110.0-111.5 ° C. ¹ HNMR δ ppm (CDCl ₃ ): 2.07 (3H, s, C H ₃ COO-), 6.14
(2H, s, -COOC H _2- ), 7.45 ~ 7.60 (4H, m, aromatic ring 2-H, 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) ν cm ^-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 added to n-hexane. The crystals were recrystallized from to obtain 12.3 g of 9-anthrylmethyl propionate as yellow needle crystals. mp. 79.0-80.0 ° C. ¹ HNMR δ ppm (CDCl ₃ ): 1.11 to 1.17 (3H, t, C H ₃ CH ₂
COO-), 2.31 to 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) ν cm ^-1 : 1738. UV (CH ₃ CN) ε (λ = 248nm): 9.82 × 10 ⁴ .

Synthesis Example 6. Synthesis of 9-anthrylmethyl p-methylbenzoate p-Methylbenzoyl chloride 13.3 instead of acetyl chloride
The reaction and post-treatment were carried out in the same manner as in Synthesis Example 4 using g (86 mmol), and 25.1 g of the obtained crude crystal was recrystallized from n-hexane to give 9-anthrylmethyl p-methylbenzoate.
8.8 g was obtained as yellow needles. mp. 123.5 ~ 124.5
° C. ¹ HNMR δppm (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) ν cm ^-1 : 1712. UV (CH ₃ CN) ε (λ = 248nm): 1.09 × 10 ⁵ .

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

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

(3) 4.0 g of poly (p-hydroxystyrene) obtained in (2) above and 1.2 g of ethyl vinyl ether were added to 1,4-
It was dissolved in 35 ml of a mixed solution of dioxane and pyridine, a catalytic amount of p-toluenesulfonic acid was added thereto, and the mixture was reacted with stirring at room temperature for 24 hours. After the reaction, inject the reaction solution into 1000 ml of water,
Crystallization was performed, and the precipitated crystals were collected by filtration, washed with water and dried under reduced pressure to give poly [p-
5.0 g of (1-ethoxyethoxy) styrene / p-hydroxystyrene] was obtained as white powder crystals. Of the obtained polymer
The constituent ratio of the p- (1-ethoxyethoxy) styrene unit and the p-hydroxystyrene unit was about 4: 6 by ¹ HNMR measurement. Weight average molecular weight of 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 the above Synthesis Example 7 and 4.8 g of 2-methoxy-1-propene were added to 1,4-
It was dissolved in 35 ml of a mixed solution of dioxane and pyridine, a catalytic amount of sulfuric acid / pyridine salt was added thereto, and the mixture was reacted with stirring at room temperature for 20 hours. After the reaction, 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 give poly {p- [2-
4.1 g of (2-methoxy) propoxy] styrene / p-hydroxystyrene} was obtained as white powder crystals. P- [2- (2-methoxy) propoxy] styrene unit of the obtained polymer
The composition ratio of p-hydroxystyrene unit was about 1: 1 based on the ¹ HNMR measurement result. 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 US 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
A polymerization reaction was carried out at 4 ° C for 4 hours. After cooling the reaction solution, it was poured into methanol for crystallization, and the precipitated crystal was collected by filtration, washed with methanol, and dried under reduced pressure to obtain 15.2 g of poly (p-tert-butoxycarbonyloxystyrene) as a white powder crystal. Weight average molecular weight of about 12000 (GPC method: polystyrene standard).

(2) 7.0 g of poly (p-tert-butoxycarbonyloxystyrene) obtained in (1) above 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 for crystallization,
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 obtained polymer
The composition ratio of the p-tert-butoxycarbonyloxystyrene unit and the p-hydroxystyrene unit was about 1: 1 from the ¹ HNMR measurement result. Weight average molecular weight of about 9500 (GPC
Method: polystyrene standard).

Synthesis Example 10. Synthesis of poly (p-vinylphenoxyacetate tert-butyl / p-hydroxystyrene) 4.0 g of poly (p-hydroxystyrene) obtained in (2) of Synthesis Example 7 above, 3.0 g of tert-butyl monochloroacetate and anhydrous carbonic acid 2.8 g of potassium was suspended in 35 ml of acetone and refluxed with stirring for 2 hours. After cooling, insoluble matter is filtered off,
The filtrate was poured into 1000 ml of water for crystallization, and the precipitated crystals were collected by filtration,
After washing with water and drying under reduced pressure, poly (p-vinylphenoxyacetic acid te
(rt-butyl / p-hydroxystyrene) (5.2 g) was obtained as white powder crystals. The composition ratio of tert-butyl p-vinylphenoxyacetate unit and p-hydroxystyrene unit of the obtained polymer was about 1: 1 by ¹ HNMR measurement. Weight average molecular weight of about 11,000 (GPC method: polystyrene standard).

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

(2) 15.0 g of poly (p-tert-butoxystyrene) obtained in (1) above was dissolved in 1,4-dioxane and concentrated hydrochloric acid was added.
20 ml was added and the mixture was reacted with stirring at 70 to 80 ° C 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 11.0 g of poly (p-tert-butoxystyrene / p-hydroxystyrene) as white powder crystals. It was The compositional ratio of p-tert-butoxystyrene unit and p-hydroxystyrene unit of the obtained polymer was about 5:95 from ¹ HNMR measurement.

(3) 8.0 g of poly (p-tert-butoxystyrene / p-hydroxystyrene) obtained in (2) above and 2.0 g of ethyl vinyl ether were dissolved in 70 ml of 1,4-dioxane, and a catalytic amount was added to the solution. P-toluenesulfonic acid pyridinium salt was added, and the mixture was reacted with stirring at room temperature for 24 hours. After the reaction, water
It was poured into 2000 ml and crystallized, and the precipitated crystals were collected by filtration, washed with water and dried under reduced pressure to give poly [p- (1-ethoxyethoxystyrene / p-
Hydroxystyrene / p-tert-butoxystyrene] 9.6
g was obtained as a white powder crystal. The composition ratio of (1-ethoxyethoxy) styrene unit to p-hydroxystyrene unit and p-tert-butoxystyrene unit of the obtained polymer was ¹ HNM.
It was about 35: 60: 5 from the 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 methyl styrene
Reaction and post-treatment are carried out in the same manner as in (1) of 1, and poly (p-
tert-butoxystyrene / p-methylstyrene) 92.3 g
Was obtained as a white powder crystal. The composition ratio of p-tert-butoxystyrene unit and p-methylstyrene unit of 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 poly (p-tert-butoxystyrene / p-methylstyrene) obtained in (1) above
Reaction and post-treatment are carried out in the same manner as in (2) of 1 above, and the precipitated crystals are collected by filtration, washed with water and dried under reduced pressure to give poly (p-methylstyrene / p-
Hydroxystyrene) (47.6 g) was obtained as white powder crystals. The composition ratio of p-methylstyrene unit and p-hydroxystyrene unit of the obtained polymer was about 5:95 from ¹ HNMR.

(3) Reaction and post-treatment were carried out in the same manner as in (3) of Synthesis Example 11 using 15.0 g of poly (p-methylstyrene / p-hydroxystyrene) obtained in (2) above and 3.5 g of ethyl vinyl ether. 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 of the obtained polymer was about 35: 60: 5 by ¹ HNMR.
Met. Weight average molecular weight of 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 75% paraformaldehyde 95.1g (2.38mol) and isopropanol 150.2g (2.50mol) to saturate it at room temperature. After stirring and reacting for 1 hour, the mixture was allowed to stand and liquid-separated, the lower layer oily matter was collected, and 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 as a colorless oily substance in a bp. 36 to 39 ° C./80 mmHg fraction. ¹ HNMR δ ppm (CDCl ₃ ): 1.16 to 1.24 (6H, d, C H ₃ ×
2), 4.01 to 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 reacted with stirring at room temperature for 5 hours. After standing overnight at room temperature, the reaction solution was poured into 400 ml of water, extracted three times with ethyl acetate (100 ml), the organic layer was washed with water (100 ml × 5), and then dried over anhydrous magnesium sulfate. The desiccant was filtered off and concentrated under reduced pressure to obtain 10.6 g of a residual acetyl compound mixture as a yellow oil. The obtained acetyl form was a mixture of mono form and di form by ¹ H NMR measurement.

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

(4) Ether mixture obtained in (3) above 10.1
g and 30 g of anhydrous potassium carbonate were suspended in 120 ml of methanol, and the mixture was reacted with stirring at room temperature for 7 hours. After standing overnight at room temperature, pour the reaction solution into 100 ml of water and wash with ethyl acetate (100 ml).
X3) Extraction was performed, the organic layer was washed with water (100 ml x 2), and then dried over anhydrous magnesium sulfate. The desiccant was filtered off and concentrated under reduced pressure to obtain 10.2 g of an oily residue. This oil was separated by column chromatography [filler: Wakogel C-200;
Eluent: n-hexane / ethyl acetate = 1/1 (v / v)]
4.5 g of 1,3-bis (isopropoxymethoxy) phenol
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 1,3-bis (isopropoxymethoxy) phenol 1.2 obtained in (4) above at 25 ° C. or below was suspended therein.
0 g (4.4 mmol) of N, N-dimethylformamide (10 m
l) The solution was added dropwise and the reaction was allowed to stir at room temperature for 2 hours. Then, the isopropoxymethyl chloride obtained in (1) above 3.6
g (33 mmol) was added dropwise at 25 ° C. or lower, and the mixture was reacted with stirring at room temperature for 3 hours. After standing overnight at room temperature, it was poured into 750 ml of water and extracted 4 times with 250 ml of ethyl acetate. 5% organic layer
4 times with 250 ml of aqueous sodium hydroxide, then 250 ml of water
It was washed 4 times with and dried over anhydrous magnesium sulfate. The desiccant was filtered off, the filtrate was concentrated under reduced pressure, and the residue was 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 obtain 1.16 g of 1,3,5-tris (isopropoxymethoxy) benzene as a pale yellow oil. ¹ HNMR δ ppm (CDCl ₃ ): 1.15 to 1.20 (18H, d, C H 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 2,2-di (4-hydroxyphenyl) propane 32.0 g (0.1
4 mol) and ethyl vinyl ether 80.8 g (1.12 mol)
Was dissolved in 130 ml of 1,4-dioxane, 2.8 g of p-toluenesulfonic acid pyridinium salt was added, and the mixture was reacted with stirring at 20 to 25 ° C for 6 hours. After the reaction, 300 ml of ethyl ether and water
100 ml was injected, and the mixture was 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 the residue 2,2-bis [4- (1-ethoxyethoxy) phenyl] propane was slightly added. Obtained as a yellow oil. ¹ HNMR δ ppm (CDCl ₃ ): 1.18 to 1.24 (6H, t, C H 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) ν cm ^-1 : 1610, 1580.

Synthesis Example 15. Synthesis of 2-cyclohexylcarbonyl-2- (p-toluenesulfonyl) propane (1) Magnesium metal (cutting) 23.9 g (0.98 gram atom) was suspended in ethyl ether, and while stirring and refluxing, bromcyclohexane 160 g (0.98). Mol) and add 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 reacted with stirring at the same temperature for 3 hours, and then left overnight at room temperature. 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 filtered off, the solvent was distilled off and the residue was distilled under reduced pressure to yield a bp. 95-100 ° C / 20mmHg fraction.
50 g of 1-cyclohexyl-2-methyl-1-propanone was obtained as a pale yellow oil. ¹ HNMR δ ppm (CDCl ₃ ): 1.06 (6H, d, C H ₃ × 2), 1.1
2 to 1.87 (10H, m, cyclohexane ring hydrogen x 5), 2.51 (1H, m, cyclohexane ring C H ), 2.76 (1H, m, C H ). IR (Neat) ν cm ^-1 : 1710.

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

(3) 2-chloro-1-cyclohexyl-2-methyl-1-propanone obtained in the above (2) 30.3 g (0.16 mol)
30.0 g (0.17 mol) of sodium p-toluenesulfinate was added to the dimethylsulfoxide (DMSO) solution of 60 ° C.
And reacted with stirring for 20 hours. Pour the reaction mixture into cold water and
After stirring at -5 ° C for 1 hour, the precipitated crystals were collected by filtration, washed with water and dried to recrystallize 18 g of crude crystals to obtain 2-cyclohexylcarbonyl-2- (p-toluenesulfonyl). ) 13.5 g of propane were obtained as white needles. mp.123-123.5 ° C. ¹ HNMR δ ppm (CDCl ₃ ): 1.19 to 1.91 (16H, m, C H ₃ × 2,
Cyclohexane ring x 5), 2.45 (3H, s, ArC H ₃ x 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 = 8Hz, aromatic ring 2-H, 6-H). IR (KBr tablets) 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 then diluted with 130 ml of 90% hydrous ethanol. Then p-toluenesulfonyl chloride at 10-25 ° C
An ethanol solution containing 60 g (0.32 mol) dissolved therein was added dropwise, and the mixture was reacted at room temperature for 2.5 hours. Then, the reaction solution was concentrated under reduced pressure, the residual oily matter was washed with water several times, and then dried over anhydrous magnesium sulfate. The desiccant was filtered off to obtain 50.7 g of p-toluenesulfonyl azide as a colorless oily substance. 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 rings 2-H, 6-H). IR (Neat) ν cm ^-1 : 2120.

(2) Cyclohexanethiol 20.2 g (0.1
A solution of 12.0 g (0.21 mol) of potassium hydroxide in ethanol (50 ml) was added dropwise to 7 mol) at room temperature, and the mixture was reacted with stirring at 30 ± 5 ° C. for 30 minutes. Then methylene chloride 18.2g (2.14mol)
Was injected and reacted at 50 ± 5 ° C. for 6 hours with stirring. After standing overnight at room temperature, 55 ml of ethanol was added to the reaction mixture to dilute it, and after adding 400 mg of sodium tungstate, 50 g (0.44 mol) of 30% hydrogen peroxide was added dropwise at 45 to 50 ° C, and at the same temperature for 4 hours. The reaction was carried out with stirring. After the reaction, 200 ml of water was poured and the mixture was left at room temperature overnight, and the precipitated crystals were collected by filtration, washed with water and dried to recrystallize 22 g of crude crystals to obtain 15.5 g of biscyclohexylsulfonylmethane as white needle crystals. It was mp.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) ν cm ^-1 : 1320, 1305.

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

Synthesis Example 17. Synthesis of bis (tert-butylsulfonyl) diazomethane (1) Synthesis example 16 was performed using 20.5 g (0.23 mol) of tert-butyl mercaptan instead of cyclohexanethiol.
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 needle crystals. mp.
152.5-155 ° C.

(2) The reaction and post-treatment were carried out in the same manner as in (3) of Synthesis Example 16 using 4.0 g (15.6 mmol) of bis (tert-butylsulfonyl) methane obtained in (1) above to obtain The crude crystals were recrystallized from ethanol to obtain 2.4 g of bis (tert-butylsulfonyl) diazomethane as pale yellow needle crystals. mp. 121-121.5 ° C. ₁ HNMR δ ppm (CDCl ₃ ): 1.52 (18 H, s, C H ₃ × 6). IR (KBr tablet) ν cm ^-1 : 2120, 1330, 1315.

Synthesis Example 18. Synthesis of 9-anthrylpropyl acetate (1) 9.6 g (0.4 gram atom) of metallic magnesium (mechanical) was suspended in tetrahydrofuran (50 ml), and 24 g (0.22 mol) of ethyl bromide was added dropwise under stirring and reflux. 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 is anthrone 1
9.4 g (0.1 mol) was added, and the mixture was stirred and refluxed for 4 hours. After cooling, pour saturated ammonium chloride aqueous solution into the reaction solution,
After extraction with ethyl ether, the ether layer was washed with water, dried over anhydrous magnesium sulfate, and then concentrated. The obtained residue
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-anthracene propanol as yellow crystals.

(2) Using 1.3 g (5.5 mmol) of 9-anthracene propanol obtained in (1) above, 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.
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 δ ppm (CDCl ₃ ): 2.24 (3H, s, C H ₃ COO-), 2.2
4 to 2.30 (2H, m, -0CH ₂ C H ₂ CH ₂ ), 3.78 to 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 = 9Hz, anthracene ring 1-H, 8-H), 8.46 (1
H, s, anthracene ring 10-H). IR (KBr tablet) ν cm ^-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 was used as propylene glycol monomethyl ether acetate 1
Dissolve in 5.0 g, pass through a 0.1 μm filter, spin coat on a silicon wafer, and heat at 90 ° C for 90 seconds.
A polymer film having a thickness of 1.0 μm was obtained. Then the developer (2.38
% Tetramethylammonium hydroxide aqueous solution) 60
It was immersed for a second by the paddle method, and the solubility of the polymer film was observed. The results are shown in Table 1.

[0131]

As is clear 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, and (3) of Synthesis Example 7, Synthesis Example 8, and Synthesis The polymers of Example 9, Synthesis Example 10, Synthesis Example 11 (3) and Synthesis Example 12 (3) are resins that are sparingly soluble in an alkaline developer.

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-UV 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 was spin-coated on a highly reflective aluminum step substrate 1 obtained by performing photolithography, etching, and aluminum sputtering on a silicon substrate.
After prebaking at 90 ° C. for 90 seconds on a hot plate, 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 of No. 3 was selectively exposed through the mask 4 (FIG. 1b). And 100 ℃, 9
After post-baking on a hot plate for 0 seconds, it was developed with an alkali developing solution (2.38% tetramethylammonium hydroxide aqueous solution) for 60 seconds to dissolve and remove only the exposed portion of the resist material 2 to obtain a positive type pattern 2a. (Fig. 1c). The obtained positive pattern had a resolution performance of 0.25 μm line and space, and had a good rectangular shape. The exposure dose 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 Biscyclohexylsulfonyl diazomethane [Synthesis Example 16 acid generator] 0.3 g 9- (2-ethoxyethoxy) methylanthracene [Synthesis Example 2 far-ultraviolet light absorber] 0.1 g Diethylene glycol dimethyl ether 13.7 g

Pattern formation was carried out in the same manner as in Example 1 using the above resist composition. As a result, 0.25 μm
A positive pattern having line-and-space resolution performance was obtained, and the shape was good with a rectangular shape. The exposure dose 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-UV absorber of Synthesis Example 1] 0.07 g ethyl lactate 13.4 g

Pattern formation was carried out in the same manner as in Example 1 using the above resist composition. As a result, 0.25 μm
A negative pattern with line-and-space resolution was obtained, and the shape was also good with a rectangular shape. The exposure dose at this time was 36 mJ / cm ² .

Examples 4-11. A resist composition having each composition shown in Tables 2 and 3 below was prepared.

[0140]

Pattern formation was performed in the same manner as in Example 1 using each of the resist compositions prepared as described above. The results are shown in Table 4.

[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

Pattern formation was carried out in the same manner as in Example 1 using the above resist composition. As a result, the lower layer of the unexposed area was partially dissolved under the influence of halation, and the positive pattern 2′a was extremely defective (FIG. 2). Such a defective pattern leads to a defect in a later process and is unusable.

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

[0146]

Example 1 using each resist composition of Table 5
A pattern was formed in the same manner as in. As a result, in all cases, the lower layer of the unexposed area was affected by halation and partly dissolved, and the pattern was extremely poor as in Comparative Example 1.
Such a defective pattern leads to a defect in a later 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 deep ultraviolet light (300 nm or less) or KrF excimer laser light (248.4 nm), such as aluminum or polysilicon. When used for highly reflective substrates such as aluminum, silicon-aluminum, aluminum-silicon-copper, or tungsten silicide, or stepped substrates, notching and halation that cause problems such as disconnection while maintaining high resolution performance and high sensitivity. A good pattern shape of quarter micron can be obtained without generating Therefore, the present invention has great value for the formation of ultrafine patterns in the semiconductor industry and the like. The resist composition of the present invention is particularly effective in pattern formation using far-ultraviolet light or KrF excimer laser light, but can be sufficiently used in pattern formation using electron beams, X-rays, etc. is there.

[0149]

[Brief description of drawings]

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

FIG. 2 is a cross-sectional view of defective pattern formation observed when a positive pattern is formed on a highly reflective substrate by using the resist composition of Comparative Example.

[Explanation of symbols]

1 ... Aluminum step substrate, 2 ... Resist material according to the present invention, 3 ... KrF excimer laser light, 4 ... Mask,
2a ... Resist pattern, 2'a ... Resist pattern.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location G03F 7/033 7/038 505 7/039 501 7/20 502 H01L 21/027 H01L 21/30 568 569 (72) Inventor Akiko Katsuyama 1006 Kadoma, Kadoma City, Osaka Prefecture Matsushita Electric Industrial Co., Ltd. (72) Kazuhiro Yamashita, 1006 Kadoma, Kadoma City, Osaka Matsushita Electric Industrial Co., Ltd.

Claims (6)

[Claims] 1. The following (i) to (iii) (i) a resin that becomes alkali-soluble by removing a protecting group by the action of an acid, (ii) an alkali-soluble resin, and a protecting group that is released by the action of an acid. And (iii) an alkali-soluble resin and a compound that crosslinks the resin by the action of an acid to make the resin hardly alkali-soluble, and a photosensitizer that generates an acid upon exposure. And a compound of the following general formula [1] [Wherein R ¹ is an alkyl group having 1 to 6 carbon atoms, and is represented by the general formula [2]: (In the formula, 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, m
Represents an integer of 0 to 3. ) Or a 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.), And n
Represents an integer of 1 to 5. ] The resist composition characterized by including 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]: [In the formula, R ⁵ and R ⁸ each independently represent a hydrogen atom or a methyl group, and R ⁶ is a tert-butoxycarbonyl group, a tert-butyl group, a tert-butoxycarbonylmethyl group, or 1-methylcyclohexyloxycarbonylmethyl. Group, tetrahydropyranyl group, 2-vinyloxyethyl group, vinyloxymethyl group, acetyl group, or the general formula [5] (In the formula, 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 ^10
12 represents a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms. ), R ⁷ is a hydrogen atom, a cyano group or a compound represented by the general formula [6] (In the formula, R ¹³ is a hydrogen atom, a halogen atom, or 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 is a hydrogen atom, a cyano group, or —COO.
Y (provided that 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 (provided that 0.2. <(K + j)
/(K+t+j)<0.8, and when j is a natural number, 0.05 ≦ j / (k + t + j) ≦ 0.50. ) Represents. ] The resist composition of Claim 1 which is a polymer shown by these. 3. A resin which becomes alkali-soluble by removing a protective group by the action of an acid in the general formula [4] is R ⁵ ,
R ⁸ and R ⁹ are hydrogen atoms, and R ⁶ is the above general formula [5].
(In the formula, R ¹⁰ , R ¹¹ and R ¹² are the same as the above.), And R ⁷ is a group represented by the general formula [6] (in the formula, R ¹³ is the same as the above). The resist composition according to claim 2, wherein the polymer is 4. The alkali-soluble resin is represented by the following general formula [7]: [In the formula, R ¹⁴ represents a hydrogen atom or a methyl group, and R ¹⁵ represents te
rt-butoxycarbonyl group, tert-butoxycarbonylmethyl group, tert-butyl group, tetrahydropyranyl group, acetyl group, or the general formula [5] (In the formula, R ¹⁰ , R ¹¹ and R ¹² are the same as above.), R ¹⁶ is a hydrogen atom, a halogen atom, or a linear or branched alkyl group 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 of Claim 1 which is a polymer shown by these. 5. The alkali-soluble resin is represented by the general formula [7].
Wherein R ¹⁴ is a hydrogen atom and R ¹⁵ is a tert-butyl group, an acetyl group, or the above general formula [5] (in the formula, 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 6. (i) a step of applying the resist composition according to claim 1 on a semiconductor substrate or the like and then heating, (ii)
Exposing to far ultraviolet light or KrF excimer laser light through a mask, and then performing heat treatment as necessary, (ii)
i) A fine pattern forming method comprising a step of developing with an alkali developing solution. [0001]