JP2847414B2 - Resist material - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a resist material used in the production of semiconductor devices and the like. Specifically, 400n as an exposure energy source
The present invention relates to a resist material for forming a positive pattern using a light source of m or less, for example, i-line light of 365 nm or far ultraviolet light of 300 nm or less, for example, a krF excimer laser of 248.4 nm.

[Prior art] In recent years, with the high-density integration of semiconductor devices, the light source of the exposure equipment used for fine processing, especially for photolithography, has become increasingly shorter in wavelength, and krF excimer laser (248.4 nm) light has been studied until now. It is becoming. However, no suitable resist material has been found yet for this wavelength.

For example, when MP2400 (manufactured by Shipley Co., Ltd.), which is said to be highly sensitive to krF excimer laser light and has good light transmittance, is used, large surface absorption of exposure light from the novolak resin itself as a base polymer and Since the photoreactivity of the naphthoquinonediazide compound as a photosensitizer is not good, the pattern shape after development is very poor and cannot be used. Also,
As a resist material using krF excimer laser light or far-ultraviolet light as a light source A resist material comprising a photosensitive compound having a group has been developed. (For example, JP-A-64-80944; JP-A-1-154048; JP-A-1-155339).

Further in the molecule Forming material made of a resin having a high light transmittance in the vicinity of the photosensitive compound and 248.4nm having a group and -SO ₂ Cl groups have also been developed. (For example, JP-A-1-188852; YT
ani et al., SPIE's 1989 Sympo., 1086-03). FIG. 4 shows a pattern forming method using this resist material. A resist material 5 is spin-coated on the semiconductor substrate 1, and 1.
A 0 μm resist material film is obtained (FIG. 4A). Note that an oxide film, a conductive film, and an insulating film are formed on the substrate 1 in many cases. Next, 248.4 nm krF excimer laser light 3
Is selectively exposed through the mask 4 (FIG. 4 (b)).
Finally, development is performed using a normal alkali developing solution (0.24% tetramethylammonium hydroxide aqueous solution) to dissolve and remove the exposed portions of the resist material 5 to obtain a pattern 5a (FIG. 4 (c)). FIG. 5 shows ultraviolet spectral curves of the resist material film (1 μm) before and after exposure. The resin used had a thickness of 1 μm and 70%, whereas the transmittance of this resist material after exposure was as low as 40%, indicating that sufficient light fading was not obtained. As a result of the pattern formation experiment, the pattern aspect ratio was about 70 degrees, and a sufficient pattern shape was not obtained. FIG. 6 shows the γ characteristics of this resist material film (1 μm). The sensitivity of this resist material was about 140 to 150 mJ / cm ² .

When using a resist material containing a photosensitive compound having a group, generally the sensitivity is approximately 100~300mJ / cm ^2,
It is difficult to use krF excimer laser light (248.4 nm), which has low energy efficiency for high output. In recent years, as a means for reducing the amount of exposure energy, a chemically amplified resist material using an acid generated by exposure as a medium has been proposed [H. Ito et al., Polym. Eng. Sci., 23
Volume, p. 1012 (1983)], and various reports have been made on this. (See, for example, WRBrunsvold et al., SPIE's 1989.
Sympo., 1086-40; T. Neenan et al., SPIE's 1989 Sympo., 10
86-01). However, the resins used in these chemically amplified resist materials are relatively inadequate in light transmittance around 248.4 nm due to having a large number of aromatic rings, or the resin has poor heat resistance. There's a problem.

As for the photosensitive compound, for example, in the case of an onium salt such as triphenylsulfonium tetrafluoroborate, solution stability is poor and the original performance is exhibited immediately after preparing a resist material, but in a semiconductor manufacturing line. It is said that it is difficult to put it to practical use,
In the case of 2,6-dinitrobenzyl sulfonic acid ester, stability as a compound is recognized, but 2-nitro-6-nitrosobenzaldehyde generated by exposure is generally used as a developer (tetramethylammonium hydroxide aqueous solution). Therefore, after development, problems such as scum remaining in the exposed portion and deterioration of the pattern shape occur. Also, tris (methanesulfonyloxy)
Benzene is not suitable as a photosensitive compound for a chemically amplified resist because benzene has a lower sensitivity than the above photosensitive compound.

[Problems to be solved by the invention] In the case of a resist material containing a photosensitive compound having a group, the photobleachability of the photosensitive compound is poor. Since the group must be photoreacted, it is difficult to obtain a good pattern shape, and a large amount of exposure energy is required. In addition, the chemically amplified resist material cannot be used unless the light transmittance around 248.4 nm of the resin is improved or the heat resistance of the resin is improved, and at the same time, the photosensitive compound can be used at a lower exposure energy amount. There is a demand for properties that generate an acid, have solution stability, and dissolve the product in a developer.

[Object of the Invention] The present invention has been made in view of the above situation, and i.
A resin that has high transparency and heat resistance after exposure to linear light or far ultraviolet light, for example, krF excimer laser light, and generates acid efficiently with high sensitivity (low exposure energy) and solution It is an object of the present invention to provide a resist material comprising a photosensitive compound which is stable in the developer and is soluble in a developer currently used.

[Constitution of the Invention] In order to achieve the above object, the present invention comprises the following constitutions.

"A heat-resistant resin composed of a component having a functional group that becomes alkali-soluble by undergoing a chemical change by heating under an acid atmosphere and a component that imparts heat resistance to the resin, and the following general formula [ A resist material comprising a photosensitive compound represented by the formula (I) or (II) and a solvent capable of dissolving both of them.

_{^{Wherein, R ▲ 1 0 ▼, R}} ▲ 2 0 ▼, R ▲ 3 0 ▼ are independently a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group, a haloalkyl group, -OR ▲ ⁷ ₀ ▼ (however, R ▲ ⁷ ₀
▼ represents a linear or branched alkyl group, an alkyl-substituted silyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, a haloalkyl group, an alkoxyalkyl group, or a linear or branched alkyloxycarbonyl group. ),
Nitro group, nitrile group, amide group or -COOR ▲ ⁸ ₀ ▼ group (wherein, R ▲ ⁸ ₀ ▼ represents. A linear or branched alkyl group) _{^{represents, R ▲ 4 0 ▼, R}} ▲ ^{_{5 0 ▼, R ▲ 6 0}} ▼ are independently a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group, a haloalkyl group, -OR ▲ ⁹ ₀ ▼ (where, R ▲ ⁹ ₀ ▼ Represents a linear or branched alkyl group.), A nitro group or a nitrile group, and n represents 2 to 4
Represents an integer. " _{^{Wherein, R ▲ 10 0 ▼ ~R ▲}} 13 0 ▼ are independently a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group, a haloalkyl group, -OR ▲ ²⁰ ₀ ▼ (although , R ▲ ²⁰ ₀ ▼ linear or branched alkyl group, alkyl-substituted silyl substituted silyl group, tetrahydropyranyl group, tetrahydrofuranyl group, a haloalkyl group, an alkoxyalkyl group, a linear or branched alkyl Represents an oxycarbonyl group.), A nitro group, a nitrile group, an amide group or -COOR
²¹ ₀ ▼ group (wherein, R ▲ ²¹ ₀ ▼ represents. A linear or branched alkyl group) _{^{represents, R ▲ 14 0 ▼ ~R ▲}} 19 0 ▼ are independently a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group, a haloalkyl group, -OR ▲ ²² ₀ ▼
(However, R ▲ ²² ₀ ▼ represents a linear or branched alkyl group.), A nitro group or a nitrile group, X is a single bond, an oxygen atom, -CH = N-group, an alkylene group, Represents a substituted alkylene group or a cycloalkylene group, m, n '
Each independently represents an integer of 1 to 4. The resist material of the present invention utilizes chemical amplification in order to reduce the amount of exposure energy as much as possible. That is, the resist material of the present invention is a component having a functional group that becomes alkali-soluble by undergoing a chemical change by heating under an atmosphere of an acid generated from an acid generator by exposure, and a component that imparts heat resistance to a resin, that is, heating. On the other hand, a feature is that a heat-resistant resin (hereinafter, abbreviated as “resin according to the present invention”) composed of a component having a function of suppressing softening of the entire resin and a novel photosensitive compound are used in combination. It is a novel resist material having: In the acid atmosphere according to the present invention, a component having a functional group that becomes alkali-soluble by heating (hereinafter referred to as a
Abbreviated as "component having a specific functional group". Examples of the) include monomers such as p-hydroxystyrene derivatives and p-hydroxy-α-methylstyrene derivatives having a protecting group capable of leaving with an acid. As a specific example, for example, p
-Methoxystyrene, p-isopropoxystyrene, p
-Tert-butoxystyrene, p-methoxymethoxystyrene, p-isopropoxymethoxystyrene, p-tetrahydropyranyloxystyrene, p-tetrahydrofuranyloxystyrene, p-trimethylsilyloxystyrene, p-tert-butoxycarbonyloxystyrene, p -Isopropoxycarbonyloxystyrene, or a p-hydroxy-α-methylstyrene derivative having the same protective group as the p-hydroxystyrene derivative, but is not limited to these. In addition, as a component that imparts heat resistance to the resin, any component may be used as long as the entire resin can be prevented from being softened by heating at 100 ° C. or higher, more preferably at 140 ° C. or higher by using this component. Are, for example, p-hydroxystyrene, p-chlorostyrene, styrene, α-methylstyrene, fumaronitrile, monoisopropyl maleate, monotert-butyl maleate, ditert-maleate
Monomers such as -butyl, monocyclohexyl maleate, maleic anhydride, N-phenylmaleimide, N-substituted phenylmaleimide, N-methylmaleimide and Nn-butylmaleimide are mentioned as more general ones.

The resin according to the present invention includes, for example, the following general formula [III] or [I
V].

Wherein R ¹ represents a methyl group, an isopropyl group, a tert-butyl group, a methoxymethyl group, an isopropoxymethyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, a trimethylsilyl group, a tert-butoxycarbonyl group or an isopropoxycarbonyl group. R ² represents a hydrogen atom, a halogen atom or a methyl group; R ³ represents a hydrogen atom, a p-hydroxyphenyl group, a p-chlorophenyl group, a phenyl group, a cyano group or —COOR ⁷ (where R ⁷ is R ⁴ and R ⁶ each independently represent a hydrogen atom, a methyl group or a halogen atom, R ⁵ represents a hydrogen atom, A cyano group or —COOR ⁸ (where R ⁸ represents a branched or cyclic alkyl group having 3 to 10 carbon atoms, or a hydrogen atom);
R ⁹ is a hydrogen atom or —COOR ¹⁰ (however, R ¹⁰ has 3 to ¹⁰ carbon atoms)
Represents a branched or cyclic alkyl group or a hydrogen atom. ), And k and l each independently represent a natural number. ] [Wherein, X represents an oxygen atom or a _{N- (CH 2) q-R} 11 ( where, R ¹¹ is have a linear, branched or cyclic alkyl group or a substituent having 1 to 10 carbon atoms Represents a good phenyl group, q represents 0 or a natural number.), L ′ and p each independently represent 0 or a natural number, and R ¹ , R ² , R ³ , R
⁴ , R ⁵ , R ⁶ , R ⁹ and k are the same as above. The compounds represented by the general formula [III] or [IV] are representative of the resin according to the present invention, but the resin according to the present invention is not limited to these compounds.

Specific examples of the resin according to the present invention include, for example, p-isopoloxystyrene and α-methylstyrene copolymer,
-Tetrahydropyranyloxystyrene and p-hydroxystyrene copolymer, p-tert-butoxystyrene and p
-Hydroxystyrene copolymer, p-tert-butoxycarbonyloxystyrene and maleic acid monocyclohexyl ester copolymer, p-tert-butoxycarbonyloxystyrene and α-methylstyrene copolymer, p-tert
-Butoxystyrene and fumaronitrile copolymer, p-methoxymethoxystyrene and p-chlorostyrene copolymer, p-methoxymethoxystyrene and maleic acid monocyclohexyl ester and maleic anhydride copolymer, p-tetrahydrofuranyloxystyrene And N-methylmaleimide copolymer, copolymer of p-tert-butoxycarbonyloxystyrene with p-hydroxystyrene and maleic anhydride, copolymerization of p-tetrahydropyranyloxystyrene with p-hydroxystyrene and fumaronitrile Copolymer, copolymer of p-tert-butoxycarbonyloxystyrene with p-hydroxystyrene and N-butylmaleimide, copolymer of p-tetrahydropyranyloxystyrene with p-hydroxystyrene and N-phenylmaleimide, etc. Including but not limited to this, and the like.

The resin according to the present invention comprises a component (monomer) having one or more components having the above-mentioned specific functional group and one or more components (monomer) for imparting heat resistance to the resin. It can be easily obtained by copolymerizing according to a conventional method. That is, one or more components (monomers) having the specific functional group and one or more components (monomers) for imparting heat resistance to the resin are, for example, benzene,
In an organic solvent such as toluene, a radical polymerization initiator [for example, azobisisobutyronitrile 2,2'-azobis (2,4-
Dimethylvaleronitrile), azo-based polymerization initiators such as 2,2'-azobis (methyl 2-methylpropionate) and peroxide-based polymerization initiators such as benzoyl peroxide and lauroyl peroxide. The polymerization reaction may be carried out in a nitrogen stream at 50 to 100 ° C. for 1 to 10 hours, and after the reaction, post-treatment may be carried out according to a conventional method for obtaining a polymer compound, and this may be isolated.

Needless to say, the resin according to the present invention can also be easily obtained by a method of appropriately introducing the specific functional group into a polymer such as commercially available poly (p-vinylphenol) by a chemical reaction.

The weight average molecular weight (▲) of the resin according to the present invention is generally about 1,000 to 40,000, preferably about 3,000 to 20,000.

At a photosensitive compound represented by the general formula [I] used in the present invention, R ▲ ¹ ₀ ▼, halogen of R ▲ ² ₀ ▼, halogen atoms and haloalkyl groups represented by R ▲ ³ ₀ ▼ is chlorine, bromine, fluorine, iodine and the like, linear, branched or cyclic alkyl group of the alkyl group, the alkyl group of the haloalkyl group, R ▲ ⁷ ₀ linear or branched alkyl represented by ▼ alkyl group, like R ▲ ⁷ ₀ ▼ alkyl group of the alkyl-substituted silyl group represented by the alkyl group of the haloalkyl group, the alkyl group of the alkyl group and alkoxy group of the alkoxyalkyl group, the linear or branched Examples of the linear or branched alkyl group of the alkyl group represented Jo of an alkyl group and R ▲ ⁸ ₀ ▼ alkyloxycarbonyl group,
For example, methyl group, ethyl group, propyl group, butyl group, amyl group, hexyl group, octyl group, decyl group, etc.
And up to 10 alkyl groups. In _{^{addition, R ▲ 4 0 ▼, R}} ▲ 5 0
▼, R ▲ ⁶ ₀ ▼ halogen atom and chlorine as the halogen of the haloalkyl group represented by, bromine, fluorine, iodine and the like, linear, branched or cyclic alkyl group of the alkyl group, alkyl haloalkyl group Examples of the linear or branched alkyl group of the alkyl group represented by group and R ▲ ⁹ ₀ ▼, such as methyl group, ethyl group, propyl group, butyl group, amyl group, a hexyl group, an octyl group, a decyl group An alkyl group having 1 to 10 carbon atoms is exemplified.

At a photosensitive compound represented by the general formula [II] is use in the present _{^{invention, R ▲ 10 0 ▼, R}} ▲ 11 0 ▼, R ▲ 12 0 ▼, halogen atoms and haloalkyl represented by R ▲ ¹³ ₀ ▼ the halogen group, chlorine, bromine, fluorine, iodine and the like, linear, branched or cyclic alkyl group of the alkyl group, the alkyl group of the haloalkyl group, linear represented by R ▲ ²⁰ ₀ ▼ or branched alkyl group of the alkyl group, like R ▲ ²⁰ ₀ ▼ alkyl group of the alkyl-substituted silyl group represented by the alkyl group of the haloalkyl group, the alkyl group of the alkyl group and alkoxy group of the alkoxyalkyl group, the alkyl group linear or branched alkyloxycarbonyl group and R ▲ ²¹
_As the alkyl group of the linear or branched alkyl group represented by ₀ ▼, for example, methyl group, ethyl group, propyl group, butyl group, amyl group, hexyl group, octyl group, decyl group, etc. And 10 alkyl groups. _{^{Also, R ▲ 14 0 ▼, R}} ▲ 15 0 ▼, R ▲ 16 0 ▼, R ▲ 17 0 ▼, R ▲ 18 0 ▼,
19R ▲ ⁴ ₀ chlorine as halogen halogen atoms and haloalkyl groups represented by ▼, bromine, fluorine, iodine and the like, linear, branched or cyclic alkyl group of the alkyl group, alkyl haloalkyl group and R ▲ the linear or branched alkyl group of the alkyl group represented ²² ₀ ▼, such as methyl group, ethyl group, propyl group, butyl group, amyl group, hexyl group, octyl group, decyl group carbon atoms And 1-10 alkyl groups. Examples of the alkylene group of the alkylene group and the substituted alkylene group represented by X include alkylene groups having 1 to 10 carbon atoms such as methylene, ethylene, propylene, butylene, pentylene, hexylene, octylene, and decylene. Examples of the cycloalkylene group include a cycloalkylene group having 3 to 10 carbon atoms such as a cyclopropylene group, a cyclopentylene group, a cyclohexylene group, a cyclooctylene group, and a cyclodecylene group. Examples thereof include halogen atoms such as chlorine, bromine, fluorine and iodine, and alkyl groups having 1 to 10 carbon atoms such as methyl, ethyl, propyl, butyl, amyl, hexyl, octyl and decyl. Is mentioned.

The inventors of the present invention have been studying a photosensitive compound that generates an acid upon exposure.Introducing a nitro group, which is an ortho-electron withdrawing group of a sulfonyl group of a benzenesulfonic acid ester, introduces a sulfonyl group due to the effect of the nitro group upon exposure. Were excited to easily dissociate the sulfonic acid ester, and it was found that nitrobenzenesulfonic acid was efficiently produced at a low exposure dose under the influence of water present in the resist film, and the present invention was completed.

The solvent used in the present invention may be any solvent that can dissolve both the resin and the photosensitive compound,
Usually, those having no absorption around 365 nm and 248.4 nm are more preferably used. More specifically, examples include, but are not limited to, ethyl cellosolve acetate, methyl cellosolve acetate, diethylene glycol dimethyl ether, ethyl lactate, methyl lactate, dioxane, and diethylene glycol monoisopropyl ether.

The resin according to the present invention does not absorb light in a wavelength region of 300 nm or more, and has extremely high light transmittance for i-line light of 365 nm. Also, it has been confirmed that an acid generator generates an acid even with i-ray light, and a chemical amplification action can be used.
Therefore, the resist material of the present invention is a resist material capable of forming a pattern using a low-exposure amount krF excimer laser beam (248.4 nm) or i-line light (365 nm) by utilizing a chemical amplification method.

"Operation" To explain the operation of the present invention, first, an acid is generated in a portion exposed to krF excimer laser light, i-ray light or the like according to, for example, a photoreaction shown in the following (A) or (B).

When heat treatment is performed after the exposure step, the functional group of the resin undergoes a chemical change by an acid according to the following reaction formula (C), becomes alkali-soluble, and elutes in a developing solution during development.

On the other hand, since no acid is generated in the unexposed portion, no chemical change occurs even when heat treatment is performed, and no alkali-soluble group is expressed. Further, since the resin itself has high heat resistance, the resin is not softened during the heat treatment. Thus, when a pattern is formed using the resist material of the present invention, a large solubility difference in an alkali developing solution occurs between an exposed portion and an unexposed portion, and the resin in the unexposed portion is heated. Since it does not soften during processing, a positive pattern having good contrast is formed as a result. Further, as shown in the reaction formula (C), the acid generated by the exposure acts as a catalyst, so that the exposure only needs to generate the necessary acid, and the amount of exposure energy can be reduced.

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples and Reference Examples, but the present invention is not limited by these.

Reference Example 1. 88 g of p-tert-butoxystyrene and fumaronitrile 3
9 g in a toluene solvent in the presence of 2,2'-azobis (methyl 2-methylpropionate) under a nitrogen stream at 90 ° C.
The polymerization reaction was carried out for an hour. After the reaction, the reaction solution was poured into methanol for crystallization, and the precipitated crystals were collected by filtration, dried and p-tert-
-Butoxystyrene-fumaronitrile copolymer (▲
▼ About 10.000) 120 g were obtained.

Example 1. A resist material having the following composition was prepared.

p-tert-butoxystyrene-fumaronitrile copolymer A pattern forming method using the above resist material will be described with reference to FIG. The resist material 2 was spin-coated on a substrate 1 such as a semiconductor and soft-baked on a hot plate at 90 ° C. for 90 seconds to obtain a resist material film having a thickness of 1.0 μm (FIG. 1A). Next, 248.4 nm krF excimer laser light 3 was selectively exposed through a mask 4 (FIG. 1B). Then, after baking on a hot plate at 130 ° C. for 90 seconds, developing with an alkaline developer (2.38% tetramethylammonium hydroxide aqueous solution) for 60 seconds,
Only the exposed portions of the resist material 2 were dissolved and removed to obtain a positive pattern 2a (FIG. 1 (c)). FIG. 2 shows ultraviolet spectral curves of the resist material film (1 μm) before and after exposure. The transmittance before and after the exposure hardly changes, and even after the exposure
High transmittance of 65%. At this time, the aspect ratio of the positive pattern was a good-shaped 0.3 μm line and space pattern of about 87 degrees. FIG. 3 shows the γ characteristics of this resist material film (1 μm). This material had high sensitivity with a minimum exposure of 21 mJ / cm ² .

Example 2 A resist material was prepared in the same manner as in Example 1 except that the resin was changed to the following styrene-based resin in Example 1, and the same experiment as in Example 1 was performed.

p-tert-butoxystyrene-p-hydroxystyrene copolymer (▲ ▼ about 13,00
0) As a result, the same good results as in Example 1 were obtained.
Positive pattern obtained using this resist material is about 18mJ
A pattern could be formed with an exposure energy of / cm ² .

Example 3 A resist material was prepared in the same manner as in Example 1 except that the photosensitive compound was changed to the following compound in Example 1, and the same experiment as in Example 1 was performed.

As a result, the same good results as in Example 1 were obtained.
Using this resist material, a positive pattern is about 15 mJ / cm ²
The pattern formation was possible with the exposure energy amount of.

Example 4 A resist material was prepared in the same manner as in Example 2 except that the photosensitive compound was changed to the following compound in Example 2, and the same experiment as in Example 2 was performed.

As a result, the same good results as in Example 2 were obtained.
The positive pattern obtained using this resist material is about 12mJ
A pattern could be formed with an exposure energy of / cm ² .

Example 5. p-Methoxymethoxystyrene-maleic acid copolymer (▲ 15,000) The same experiment as in Example 1 was performed using the resist material prepared with the above composition.

 As a result, it has value.

The resist material is particularly effective for i-ray light, far ultraviolet light, and krF excimer laser light, but can be sufficiently used for electron beams and Χ rays.

[Brief description of the drawings]

1 to 3 show the results obtained in Example 1, and FIG.
FIG. 2 is a cross-sectional view of a process for forming a pattern using the resist material of the present invention, FIG. 2 is an ultraviolet spectrum curve of the resist material of the present invention (the solid line is before exposure, and the broken line is after exposure);
The figure shows a γ characteristic diagram of the resist material of the present invention. The fourth
FIG. 5 is a cross-sectional view of a process for forming a pattern using a conventional resist material, FIG. 5 is an ultraviolet spectrum curve of the conventional resist material (solid line before exposure, broken line after exposure), and FIG. FIG. 4 is a γ characteristic diagram of a resist material. 1 ... substrate, 2 ... resist material film of the present invention, 3 ... kr
F excimer laser beam, 4... Mask, 5... Conventional resist material film, 2a... Pattern obtained by the resist material film of the present invention, 5a... Pattern obtained by the conventional resist material film.

──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Keiji Ohno Saitama Prefecture Kawagoe City, Ogata 1633 Wako Jun Pharmaceutical Co., Ltd. Tokyo Research Division (56) References JP-A-61-3141 (JP, A) (58) Field surveyed (Int. Cl. ⁶ , DB name) G03F ^7/ 00-7/18

Claims (3)

(57) [Claims] 1. A heat-resistant resin composed of a component having a functional group that becomes alkali-soluble by undergoing a chemical change by heating in an acid atmosphere and a component that imparts heat resistance to the resin, and generates an acid upon exposure. A resist material comprising a photosensitive compound represented by the following general formula [I] or [II], and a solvent capable of dissolving both of them. _{^{Wherein, R ▲ 1 0 ▼, R}} ▲ 2 0 ▼, R ▲ 3 0 ▼ are independently a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group, a haloalkyl group, -OR ▲ ⁷ ₀ ▼ (however, R ▲ ⁷ ₀
▼ represents a linear or branched alkyl group, an alkyl-substituted silyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, a haloalkyl group, an alkoxyalkyl group, or a linear or branched alkyloxycarbonyl group. ),
Nitro group, nitrile group, amide group or -COOR ▲ ⁸ ₀ ▼ (where, R ▲ ⁸ ₀ ▼ represents. A linear or branched alkyl group) _{^{represents, R ▲ 4 0 ▼, R}} ▲ 5 ₀ ▼, R ▲ ⁶ ₀ ▼ are independently a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group, a haloalkyl group, -OR ▲ ⁹ ₀ ▼ (where, R ▲ ⁹ ₀ ▼ is Represents a linear or branched alkyl group), a nitro group or a nitrile group, and n represents 2 to 4
Represents an integer. ] _{^{Wherein, R ▲ 10 0 ▼ ~R ▲}} 13 0 ▼ are independently a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group, a haloalkyl group, -OR ▲ ²⁰ ₀ ▼ (although , R ▲ ²⁰ ₀ ▼ linear or branched alkyl group, an alkyl-substituted silyl group, tetrahydropyranyl group, tetrahydrofuranyl group, a haloalkyl group, an alkoxyalkyl group, a linear or branched alkyloxycarbonyl Represents a group.),
Nitro group, nitrile group, amide group or -COOR ▲ ²¹ ₀ ▼ group (wherein, R ▲ ²¹ ₀ ▼ represents. A linear or branched alkyl group) represents, R ▲ ¹⁴ ₀ ▼ ~R ▲ ¹⁹⁰ ₀ ▼ are each independently a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group, a haloalkyl group, -OR ▲ ²² ₀ ▼ (however,
R ▲ ²² ₀ ▼ represents a linear or branched alkyl group. ), A nitro group or a nitrile group, X represents a single bond, an oxygen atom, a -CH = N- group, an alkylene group, a substituted alkylene group or a cycloalkylene group, and m and n 'each independently represent 1 to 4 Represents an integer. ] 2. A heat-resistant resin comprising a component having a functional group which becomes alkali-soluble by undergoing a chemical change upon heating in an acid atmosphere and a component which imparts heat resistance to the resin, has the following general formula [III]: Wherein R ¹ represents a methyl group, an isopropyl group, a tert-butyl group, a methoxymethyl group, an isopropoxymethyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, a trimethylsilyl group, a tert-butoxycarbonyl group or an isopropoxycarbonyl group. R ² represents a hydrogen atom, a halogen atom or a methyl group; R ³ represents a hydrogen atom, a p-hydroxyphenyl group, a p-chlorophenyl group, a phenyl group, a cyano group or —COOR ⁷ (where R ⁷ is R ⁴ and R ⁶ each independently represent a hydrogen atom, a methyl group or a halogen atom, R ⁵ represents a hydrogen atom, A cyano group or —COOR ⁸ (where R ⁸ represents a branched or cyclic alkyl group having 3 to 10 carbon atoms or a hydrogen atom), and R ⁹ represents a hydrogen atom or —COOR ¹⁰ ( However, R ¹⁰ has 3 carbon atoms
Represents up to 10 branched or cyclic alkyl groups, or a hydrogen atom. ), And k and l each independently represent a natural number]. 3. A heat-resistant resin composed of a component having a functional group which becomes alkali-soluble by undergoing a chemical change by heating in an acid atmosphere and a component which imparts heat resistance to the resin is represented by the following general formula [IV]: [In the formula, X is an oxygen atom or N- (CH ₂ ) q-R ¹¹ (provided that
R ¹¹ represents a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms or a phenyl group which may have a substituent, and q represents 0 or a natural number. 1 ′ and p each independently represent 0 or a natural number, and R ¹ , R ² , R ³ , R ⁴ ,
R ⁵ , R ⁶ , R ⁹ and k are the same as above. The resist material according to claim 1, which is a resin represented by the formula: