JP2002107932A - Radiation sensitive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a high sensitivity radiation sensitive composition having such a resolution as to enable very fine patterning. SOLUTION: The radiation sensitive composition contains a siloxane polymer having a fluorine-containing substituent and an acid generating agent which generates an acid when irradiated with radiation or the radiation sensitive composition contains a siloxane polymer having a fluorine-containing substituent and a base generating agent which generates a base when irradiated with a radiation.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a radiation-sensitive composition used for producing semiconductor integrated circuits, lithography masks and the like.

[0002]

2. Description of the Related Art In recent years, in fields such as the manufacture of semiconductor circuits and lithography masks, patterns have been miniaturized with an increase in the degree of integration. In order to realize this, a resist material having a higher resolution has been required, and it has been required that a very fine pattern can be processed with high sensitivity. Furthermore, in the conventional lithography using a relatively long wavelength light source,
It is difficult to perform such fine processing, and lithography using vacuum ultraviolet rays, X-rays, or electron beams having shorter wavelengths is being studied, and resists corresponding to such light sources are required.

Conventionally, a chemically amplified resist has been actively studied as a known resist material having high sensitivity and high resolution used in lithography using ultraviolet light as a light source. A chemically amplified resist is a resist having a mechanism in which an acid is generated in an exposed portion by the action of a photoacid generator, and the solubility of the exposed portion is changed by the catalytic action of the acid. Conventionally,
Among such chemically amplified resists, those showing relatively good resist performance, as a resin component, a resin in which an alkali-affinity group in an alkali-soluble resin is protected with a t-butyl ester group or a t-butoxycarbonyl group, A resist using a resin similarly protected by a silyl group, a resin similarly protected by a ketal group, a resin similarly protected by an acetal group, a resin containing a (meth) acrylic acid component, and the like are known.

Japanese Patent Application Laid-Open No. 6-273936 discloses a pattern forming method using a siloxane polymer.

[0005]

However, it is difficult for a styrene-based, acrylic-based, or siloxane-based polymer used in a conventional resist to absorb fine vacuum ultraviolet rays having a short wavelength, and to form a fine pattern. could not.

[0006]

The present inventors have found that a siloxane polymer having a fluorine-containing substituent has high transmittance to vacuum ultraviolet rays and exhibits high performance as a resist material. Reached.

That is, one aspect of the present invention is a radiation-sensitive composition comprising a siloxane polymer having a fluorine-containing substituent and an acid generator that generates an acid upon irradiation with radiation, Another embodiment of the present invention is a radiation-sensitive composition containing a siloxane polymer having a fluorine-containing substituent and a base generator that generates a base upon irradiation with radiation.

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The siloxane polymer used in the radiation-sensitive composition of the present invention only needs to have a fluorine-containing substituent, and usually hydrolyzes a silane compound represented by the general formula (1). It can be obtained by condensation polymerization.

[Rf _{X RY} SiA _(4-XY) ] (1) (where Rf is a monovalent organic group containing fluorine, R is hydrogen, an alkyl group, an alkenyl group, an aryl group, or a substituted product thereof) And A represents a hydrolyzable group.When there are a plurality of Rf or R, they may be the same or different, X is an integer of 1 to 3, Y is an integer of 0 to 2, X + Y ≦ 3).

A copolymer obtained by subjecting the silane compound represented by the general formula (2) to hydrolysis and condensation polymerization together with the general formula (1) is more preferably used.

[R _Z SiA _(4-Z) ] (2) (where R represents hydrogen, an alkyl group, an alkenyl group, an aryl group, or a substituted product thereof, and A represents a hydrolyzable group. R may be the same or different, and Z is an integer of 0 to 3.)

Specific examples of Rf in the general formula (1) include a 2,2,2-trifluoroethyl group, a 2,2,3,3-tetrafluoropropyl group, and a 3,3,3-trifluoro group. Propyl group, 2,2,3,
3,3-pentafluoropropyl group, 3,3,4,4,4-pentafluorobutyl group, 2,2,3,3,4,4,4-heptafluorobutyl group, 3,3,4,4 , 5,5,5-heptafluoropentyl group, 2,2,3,
3,4,4,5,5,5-nonafluoropentyl group, 3,3,4,4,5,5,6,
6,6-nanofluorohexyl group, undecafluoro-1,1-
Dihydrohexyl group, undecafluoro-1,1,2,2-tetrahydroheptyl group, tridecafluoro-1,1-dihydroheptyl group, tridecafluoro-1,1,2,2-tetrahydrooctyl group, Pentadecafluoro-1,1-dihydrooctyl group, pentadecafluoro-1,1,2,2-tetrahydrononyl group, heptadecafluoro-1,1-dihydrononyl group, heptadecafluoro-1,1,2, 2-tetrahydrodecyl group, nonadecafluoro-1,1-dihydrodecyl group, (3-heptafluoroisopropoxy) propyl group, 2-fluorophenylpropyl group, 3-fluorophenylpropyl group, 4-fluorophenylpropyl group, 2,3-difluorophenylpropyl group, 2,4-difluorophenylpropyl group, 2,5-difluorophenylpropyl group, 2,6-difluorophenylpropyl group, 3,4-difluorophenylpropyl group, 3,5-diflur Orophenylpropyl group, 2,3,4-trifluorophenylpropyl group, 2,3,5-trifluorophenylpropyl group, 2,3,6-trifluorophenylpropyl group, 2,4,5-trifluorophenylpropyl Group, 2,4,6-trifluorophenylpropyl group, 3,4,5-trifluorophenylpropyl group, pentafluorophenylpropyl group, 2- (trifluoromethyl) phenylpropyl group, 3- (trifluoromethyl ) Phenylpropyl group, 4- (trifluoromethyl) phenylpropyl group, 3,5-bis (trifluoromethyl) phenylpropyl group, 2,4-bis (trifluoromethyl) phenylpropyl group, 2-fluorophenethyl group ,
3-fluorophenethyl group, 4-fluorophenethyl group, 2,
3-difluorophenethyl group, 2,4-difluorophenethyl group, 2,5-difluorophenethyl group, 2,6-difluorophenethyl group, 3,4-difluorophenethyl group, 3,5-difluorophenethyl group, 2,3, 4-trifluorophenethyl group, 2,
3,5-trifluorophenethyl group, 2,3,6-trifluorophenethyl group, 2,4,5-trifluorophenethyl group, 2,4,6-
Trifluorophenethyl group, 3,4,5-trifluorophenethyl group, pentafluorophenethyl group, 2- (trifluoromethyl) phenethyl group, 3- (trifluoromethyl) phenethyl group, 4- (trifluoromethyl) phenethyl group , A 3,5-bis (trifluoromethyl) phenethyl group,
2,4-bis (trifluoromethyl) phenethyl group, 2-fluorobenzyl group, 3-fluorobenzyl group, 4-fluorobenzyl group, 2,3-difluorobenzyl group, 2,4-difluorobenzyl group, 2,5 -Difluorobenzyl group, 2,6-difluorobenzyl group, 3,4-difluorobenzyl group, 3,5-difluorobenzyl group, 2,3,4-trifluorobenzyl group, 2,3,
5-trifluorobenzyl group, 2,3,6-trifluorobenzyl group, 2,4,5-trifluorobenzyl group, 2,4,6-trifluorobenzyl group, 3,4,5-trifluorobenzyl group Pentafluorobenzyl group, 2- (trifluoromethyl) benzyl group, 3- (trifluoromethyl) benzyl group, 4- (trifluoromethyl) benzyl group, 3,5-bis (trifluoromethyl) benzyl group, 2 , 4-bis (trifluoromethyl) benzyl group, 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 2,3-difluorophenyl group, 2,4-difluorophenyl group, 2,5- Difluorophenyl group, 2,6-difluorophenyl group, 3,4-difluorophenyl group, 3,5-difluorophenyl group, 2,3,4-trifluorophenyl group, 2,3,5-trifluorophenyl group, 2,
3,6-trifluorophenyl group, 2,4,5-trifluorophenyl group, 2,4,6-trifluorophenyl group, 3,4,5-trifluorophenyl group, pentafluorophenyl group, 2- ( (Trifluoromethyl) phenyl group, 3- (trifluoromethyl) phenyl group, 4- (trifluoromethyl) phenyl group, 3,5-bis (trifluoromethyl) phenyl group, 2,4-
Examples thereof include, but are not limited to, a bis (trifluoromethyl) phenyl group.

Specific examples of the alkyl group represented by R in the general formula (1) or (2) and derivatives thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group and a hexyl group. Heptyl, octyl, nonyl, decyl, undecyl, dodecyl, cyclohexyl, 2- (3,4-epoxycyclohexyl) ethyl, 3-glycidoxypropyl, 3-aminopropyl, 3-cyanopropyl group, dichloromethyl group, 3-
Examples include, but are not limited to, chloropropyl, mercaptomethyl, mercaptopropyl, methacryloxypropyl, acryloxypropyl, and benzyl groups. Specific examples of the alkenyl group and its derivative include a vinyl group, an allyl group, a 1,7-octadienyl group, a 2,4-pentadienyl group, a 1-chloromethylethenyl group, and a 2- (3-cyclohexenyl) ethyl group And the like, but are not limited thereto. Specific examples of the aryl group and derivatives thereof include, but are not limited to, a phenyl group, a p-tolyl group, a chlorophenyl group, a dichlorophenyl group, and a naphthyl group. Specific examples of A in the general formula (1) or (2) include a hydrolyzable group such as a methoxy group, an ethoxy group, a methoxyethoxy group, a chlorine atom, a bromine atom, an acetoxy group, and a methylethylketoxime group. But not limited to these.

As specific examples of the silane compound represented by the general formula (1), pentafluorophenylpropyldimethylchlorosilane, pentafluorophenylpropylmethyldichlorosilane, pentafluorophenylpropyltrichlorosilane, pentafluorophenylpropyldimethylmethoxysilane, pentafluorophenylpropysilane Methyldimethoxysilane, pentafluorophenylpropyltrimethoxysilane, bis (pentafluorophenylpropyl) dimethoxysilane, 4-fluorophenylpropyltrichlorosilane, 4-fluorophenylpropyltrimethoxysilane, 3,5-difluorophenylpropyltrichlorosilane, 3,5- Difluorophenylpropyltrimethoxysilane, 2,4,6-trifluorophenylpropyltrichlorosilane, 2,4,6-to Fluorophenylpropyltrimethoxysilane, pentafluorophenyldimethylchlorosilane, pentafluorophenylmethyldichlorosilane, pentafluorophenyltrichlorosilane, pentafluorophenyldimethylmethoxysilane, pentafluorophenylmethyldimethoxysilane, pentafluorophenyltrimethoxysilane, 4-fluorophenyl Trichlorosilane, 4-fluorophenyltrimethoxysilane, 3,5-difluorophenyltrichlorosilane, 3,5-
Difluorophenyltrimethoxysilane, 2,4,6-trifluorophenyltrichlorosilane, 2,4,6-trifluorophenyltrimethoxysilane, 2,3,4-trifluorobenzyltrichlorosilane, 2,3,4-trichlorosilane Fluorobenzyltrimethoxysilane, pentafluorobenzyltrichlorosilane, pentafluorobenzyltrimethoxysilane,
2,3,4-trifluorophenethyltrichlorosilane, 2,3,
4-trifluorophenethyltrimethoxysilane, pentafluorophenethyltrichlorosilane, pentafluorophenethyltrimethoxysilane, 3,3,3-trifluoropropyldimethylchlorosilane, 3,3,3-trifluoropropylmethyldichlorosilane, 3,3 , 3-trifluoropropyltrichlorosilane, bis (3,3,3-trifluoropropyl) dichlorosilane, tris (3,3,3-trifluoropropyl) chlorosilane, 3,3,3-trifluoropropyldimethylethoxysilane , 3,3,3-trifluoropropylmethyldiethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, bis (3,3,3- Fluoropropyl) diethoxysilane, tris (3,3,3-trifluoropropyl)
Ethoxysilane, 3,3,3-trifluoropropyldiphenylethoxysilane, 3,3,3-trifluoropropylphenyldiethoxysilane, 3,3,3-trifluoropropylmethylphenylchlorosilane, 3,3,3-trisilane Fluoropropylmethylphenylethoxysilane, 3,3,4,4,5,5,6,6,6-nanofluorohexylmethyldichlorosilane, 3,3,4,4,5,
5,6,6,6-nanofluorohexyltrichlorosilane, 3,3,
4,4,5,5,6,6,6-nanofluorohexylmethyldiethoxysilane, 3,3,4,4,5,5,6,6,6-nanofluorohexyltriethoxysilane, tridecafluoro -1,1,2,2-tetrahydrooctyltrichlorosilane, tridecafluoro-1,
1,2,2-tetrahydrooctyltriethoxysilane, heptadecafluoro-1,1,2,2-tetrahydrodecyldimethylchlorosilane, heptadecafluoro-1,1,2,2-tetrahydrodecylmethyldichlorosilane, heptadecafluoro
-1,1,2,2-tetrahydrodecyltrichlorosilane, heptadecafluoro-1,1,2,2-tetrahydrodecyldimethylmethoxysilane, heptadecafluoro-1,1,2,2-tetrahydrodecylmethyldimethoxysilane, Heptadecafluoro-1,1,2,2-tetrahydrodecyltriethoxysilane, 3- (heptafluoroisopropoxy) propyltrichlorosilane, 3- (heptafluoroisopropoxy) propyltriethoxysilane and the like can be mentioned. It is not limited to. These silane compounds may be used alone or as a mixture of two or more.

Specific examples of the compound represented by the general formula (2) include tetramethoxysilane, tetraethoxysilane, tetraacetoxysilane, tetrachlorosilane,
Methyltrimethoxysilane, methyltriethoxysilane, methyltriacetoxysilane, methyltris (methoxyethoxy) silane, methyltris (methylethylketoxime) silane, methyltrichlorosilane, phenyltrimethoxysilane, phenyltriethoxysilane,
Phenyltriacetoxysilane, phenyltris (methoxyethoxy) silane, phenyltris (methylethylketoxime) silane, phenyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane,
Examples thereof include dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-aminopropyltriethoxysilane, and 3-methacryloxypropyltrimethoxysilane. These silane compounds may be used alone or as a mixture of two or more.

A siloxane polymer is obtained by adding water to these silane compounds and subjecting them to hydrolysis and partial condensation. The water used is preferably ion-exchanged water, and the amount thereof is preferably in the range of 1 to 4 moles per 1 mole of the silane compound.

The reaction for obtaining the siloxane polymer may be carried out without a solvent, but is usually carried out in a solvent. As the solvent, an organic solvent is preferable, methyl isobutyl ketone,
Diisobutyl ketone, diethyl ether, ethyl acetate,
Hexane, cyclohexane, normal butanol and the like can be preferably used. The amount of the solvent can be arbitrarily selected, but is preferably from 0.1 to 1 part by weight of the silane compound.
It is preferably used in the range of 3.0 parts by weight. At this time, an acid or base catalyst can be used,
Acid catalysts are preferred. As specific examples, hydrochloric acid, sulfuric acid, acetic acid,
In addition to trifluoroacetic acid, phosphoric acid, etc., solid acids such as ion exchange resins are also included.

The reaction temperature is usually selected from the range of the freezing point to the boiling point of the reaction system. To obtain a high-molecular-weight siloxane polymer, the reaction is preferably carried out under reflux for 1 to 100 hours. In addition, heating or addition of a base catalyst can be performed to increase the degree of polymerization of the siloxane polymer.

From the viewpoint of pattern processability, the siloxane polymer is preferably made alkali-soluble. When the purpose is to make the siloxane polymer alkali-soluble, it is necessary to pay attention to increasing the degree of polymerization excessively because the number of hydroxysilyl groups becomes insufficient and the solubility in alkali decreases. . Also, applicability,
To improve storage stability, it is preferable to remove water and the catalyst from the reaction solution. The method of removing is not particularly limited, for example, can be performed using an adsorbent such as ion exchange resin, ion exchange fiber, molecular sieve and a desiccant, preferably, methyl isobutyl ketone, diisobutyl ketone, diethyl ether A siloxane polymer is extracted from the reaction solution by using a hydrophobic organic solvent such as the above, and the organic layer is washed with water.

Of the siloxane polymers obtained by polymerizing the silane compounds represented by the general formulas (1) and (2), a silsesquioxane polymer is particularly preferably used. Since the silsesquioxane polymer is easily obtained in an alkali-soluble state and has a high glass transition point, a resist with high sensitivity and high resolution can be obtained. The silsesquioxane polymer can be obtained by using a compound containing three hydrolyzable groups A among the silane compounds represented by the general formulas (1) and (2).

When the compounds represented by the general formulas (1) and (2) are mixed and polymerized, the preferable molar fraction of the general formula (1) is from 0.5 mol% to 80 mol%, Preferably it is 2 mol% to 60 mol%, more preferably 5 mol% to 50 mol%. If the amount of the compound represented by the general formula (1) is too small, the light transmittance of the resist film decreases.

The radiation-sensitive composition of the present invention contains an acid generator which generates an acid upon irradiation with a radiation or a base generator which generates a base upon irradiation with a radiation.

Any known acid generator can be preferably used in the present invention. Specific examples of the acid generator include an onium salt, a halogen-containing compound, a diazoketone compound, a diazomethane compound, a sulfone compound, a sulfonate compound, and a sulfonimide compound.

Specific examples of onium salts include diazonium salts, ammonium salts, iodonium salts, sulfonium salts, phosphonium salts, oxonium salts and the like. Preferred onium salts include diphenyliodonium triflate, diphenyliodonium pyrene sulfonate, diphenyliodonium dodecylbenzenesulfonate, triphenylsulfonium triflate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium naphthalenesulfonate, (hydroxyphenyl) benzylmethylsulfonium toluenesulfonate And the like.

Specific examples of the halogen-containing compound include a haloalkyl group-containing hydrocarbon compound and a haloalkyl group-containing heterocyclic compound. Preferred halogen-containing compounds include 1,1-bis (4-chlorophenyl) -2,2,2-trichloroethane, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, and 2-naphthyl-4,6. -Bis (trichloromethyl)
-S-triazine and the like.

Specific examples of the diazoketone compound include a 1,3-diketo-2-diazo compound, a diazobenzoquinone compound, and a diazonaphthoquinone compound. Preferred diazoketone compounds are 1,2-naphthoquinonediazido-4-sulfonic acid and 2,2,3,4,4 '
Esters with tetrahydroxybenzophenone, 1,
2-naphthoquinonediazide-4-sulfonic acid and 1,1,
Examples thereof include esters with 1-tris (4-hydroxyphenyl) ethane.

Specific examples of the diazomethane compound include bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane,
Bis (phenylsulfonyl) diazomethane, bis (p-
Tolylsulfonyl) diazomethane, bis (2,4-xylylsulfonyl) diazomethane, bis (p-chlorophenylsulfonyl) diazomethane, methylsulfonyl-p
-Toluenesulfonyldiazomethane, cyclohexylsulfonyl (1,1-dimethylethylsulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, phenylsulfonyl (benzoyl) diazomethane and the like.

Specific examples of the sulfone compound include β
-Ketosulfone compounds, β-sulfonylsulfone compounds and the like. Preferred compounds include 4-trisphenacylsulfone, mesitylphenacylsulfone,
Bis (phenylsulfonyl) methane and the like can be mentioned.

Examples of the sulfonic acid ester compound include:
Examples thereof include alkylsulfonic acid esters, haloalkylsulfonic acid esters, arylsulfonic acid esters, and iminosulfonates. Specific examples of the sulfonic acid compound include benzoin tosylate, α-methylol benzoin tosylate, 2,6-dinitrobenzyl tosylate, 2-nitrobenzyl tosylate, 4-nitrobenzyl tosylate, pyrogallol trimesylate, nitrobenzyl And -9,10-diethoxyanthracene-2-sulfonate.

Specific examples of the sulfonimide compound include N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, and N- ( Trifluoromethylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-
(Trifluoromethylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] Heptane-5,6
-Oxy-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) naphthyldicarboximide, N- (camphasulfonyloxy) succinimide, N- (camphasulfonyloxy) phthalimide, N- (camphasulfonyloxy) Diphenylmaleimide, N- (camphasulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (camphasulfonyloxy) -7-
Oxabicyclo [2.2.1] hept-5-ene-2,
3-dicarboximide, N- (camphasulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide, N- (camphasulfonyloxy) naphthyldicarboximide, N
-(4-methylphenylsulfonyloxy) succinimide, N- (4-methylphenylsulfonyloxy) phthalimide, N- (4-methylphenylsulfonyloxy) diphenylmaleimide, N- (4-methylphenylsulfonyloxy) bicyclo [2. 2.1] Hept-5
-Ene-2,3-dicarboximide, N- (4-methylphenylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- ( 4-methylphenylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide, N- (4-methylphenylsulfonyloxy) naphthyldicarboximide, N- (2 -Trifluoromethylphenylsulfonyloxy) succinimide, N- (2-trifluoromethylphenylsulfonyloxy) phthalimide, N- (2
-Trifluoromethylphenylsulfonyloxy) diphenylmaleimide, N- (2-trifluoromethylphenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2
-Trifluoromethylphenylsulfonyloxy) -7
-Oxabicyclo [2.2.1] hept-5-ene-
2,3-dicarboximide, N- (2-trifluoromethylphenylsulfonyloxy) bicyclo [2.
2.1] Heptane-5,6-oxy-2,3-dicarboximide, N- (2-trifluoromethylphenylsulfonyloxy) naphthyldicarboximide, N-
(4-fluorophenylsulfonyloxy) succinimide, N- (2-fluorophenylsulfonyloxy)
Phthalimide, N- (4-fluorophenylsulfonyloxy) diphenylmaleimide, N- (4-fluorophenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-
(4-Fluorophenylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-
Dicarboximide, N- (4-fluorophenylsulfonyloxy) bicyclo [2.2.1] heptane-
5,6-oxy-2,3-dicarboximide, N-
(4-Fluorophenylsulfonyloxy) naphthyldicarboximide and the like can be mentioned.

As the base generator in the present invention, any known base generator can be preferably used. Examples thereof include transition metal complexes such as cobalt, orthonitrobenzyl carbamates, α, α-dimethyl-3,5-dimethoxybenzyl carbamates, and acyloxyiminos. As the type of the base generated by irradiation, any of organic and inorganic bases can be preferably used, but the generation efficiency by irradiation, the catalytic effect in the polymerization of the siloxane polymer, the solubility in the siloxane polymer solution, etc. In view of this, organic amines are particularly preferred. The type of organic amines generated may be either aliphatic or aromatic, and may be monofunctional or polyfunctional. Specific examples of amines generated by ultraviolet irradiation include ammonia, methylamine, ethylamine,
Propylamine, butylamine, hexylamine, cyclohexylamine, decylamine, cetylamine, hydrazine, tetramethylenediamine, hexamethylenediamine, benzylamine, aniline, naphthylamine, phenylenediamine, toluenediamine, diaminodiphenylmethane, hexamethyltetramine, piperidine, piperazine, etc. Can be listed.

Specific examples of preferred base generators include bromopentaammonium cobalt perchlorate, bromopentamethylamine cobalt perchlorate, bromopentapropylamine cobalt perchlorate, hexaammonium cobalt perchlorate, Transition metal complexes such as hexamethylamine cobalt perchlorate and hexapropylamine cobalt perchlorate, [[(2-nitrobenzyl) oxy] carbonyl] methylamine, [[(2-nitrobenzyl) oxy] carbonyl] Propylamine, [[(2-nitrobenzyl) oxy] carbonyl] hexylamine,
[[(2-nitrobenzyl) oxy] carbonyl] cyclohexylamine, [[(2-nitrobenzyl) oxy] carbonyl] aniline, [[(2-nitrobenzyl) oxy] carbonyl] piperidine, bis [[(2-
Nitrobenzyl) oxy] carbonyl] hexamethylenediamine, bis [[(2-nitrobenzyl) oxy] carbonyl] phenylenediamine, bis [[(2-nitrobenzyl) oxy] carbonyl] toluenediamine, bis [[(2-nitro Benzyl) oxy] carbonyl] diaminodiphenylmethane, bis [[(2-nitrobenzyl) oxy] carbonyl] piperazine, [[(2,6-
[Dinitrobenzyl) oxy] carbonyl] methylamine, [[(2,6-dinitrobenzyl) oxy] carbonyl] propylamine, [[(2,6-dinitrobenzyl) oxy] carbonyl] hexylamine, [[(2,6-dinitrobenzyl) oxy] carbonyl] hexylamine
6-dinitrobenzyl) oxy] carbonyl] cyclohexylamine, [[(2,6-dinitrobenzyl) oxy] carbonyl] aniline, [[(2,6-dinitrobenzyl) oxy] carbonyl] piperidine, bis [[(2 6-dinitrobenzyl) oxy] carbonyl] hexamethylenediamine, bis [[(2,6-dinitrobenzyl) oxy] carbonyl] phenylenediamine, bis [[(2,6-dinitrobenzyl) oxy] carbonyl] toluenediamine, bis Orthonitrobenzyl carbamates such as [[(2,6-dinitrobenzyl) oxy] carbonyl] diaminodiphenylmethane, bis [[(2,6-dinitrobenzyl) oxy] carbonyl] piperazine, [[(α, α-dimethyl- 3,5-
Dimethoxybenzyl) oxy] carbonyl] methylamine, [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] propylamine,
[[(Α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] hexylamine, [[(α,
α-dimethyl-3,5-dimethoxybenzyl) oxy]
Carbonyl] cyclohexylamine, [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] aniline, [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] piperidine,
Bis [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] hexamethylenediamine,
Bis [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] phenylenediamine, bis [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] toluenediamine, bis [ [(Α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] diaminodiphenylmethane,
Α, α- such as bis [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] piperazine
Dimethyl-3,5-dimethoxybenzyl carbamates, propionyl acetophenone oxime, propionyl benzophenone oxime, propionyl acetone oxime, butyryl acetophenone oxime, butyryl benzophenone oxime, butyryl acetone oxime, adipoyl acetophenone oxime, adipoyl benzophenone oxime, Acyloxyiminos such as adipoylacetone oxime, acroylacetophenone oxime, acroylbenzophenone oxime, and acroylacetone oxime can be mentioned, but are not limited thereto.

Among the above-mentioned ultraviolet base generators, particularly preferable ones are [[(2-nitrobenzyl) oxy] carbonyl] cyclohexylamine and bis [[(2
-Nitrobenzyl) oxy] carbonyl] hexamethylenediamine and bis [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] hexamethylenediamine.

These base generators or acid generators can be used alone or in combination of two or more. The addition amount of the base generator or the acid generator is usually 0.001 to 50% by weight based on the polymer, more preferably 0.01 to 50% by weight.
1 to 15% by weight, more preferably 0.1 to 10% by weight
% By weight.

A sensitizer can be added to the composition of the present invention, if necessary. Examples of the sensitizer include Michler's ketone, N-phenylglycine, aromatic amines such as N-phenyldiethanolamine, azidoanthraquinone, aromatic monoazides such as azidobenzalacetophenone,
3,3'-carbonylbis (diethylaminocoumarin)
For example, any of those generally used for a photocurable resin and those used as a charge transfer agent for electrophotography can be preferably used. When a sensitizer is used, it is preferably added in the range of 0.1 to 5% by weight based on the siloxane polymer. If the ratio is out of this range, the photosensitivity is lowered and the mechanical properties of the polymer are lowered.

[0036] In addition to the sensitizer, additives such as a stabilizer, an antifoaming agent and an acid diffusion inhibitor can be added to the radiation-sensitive composition of the present invention, if necessary.

The radiation-sensitive composition of the present invention can be obtained by dissolving the above components in a solvent. The amount of the solvent used is not particularly limited, but the solid content is 0.5 to 35% by weight.
Preferably, it is adjusted so that Preferred solvents used are ethyl acetate, butyl acetate, amyl acetate, ethyl propionate, methyl butyrate, methyl benzoate, methyl lactate, ethyl lactate, ethyl pyruvate, β-
Esters such as methyl isobutylate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, and γ-butyrolactone; cellosolves such as methyl cellosolve, ethyl cellosolve, and butyl cellosolve; methyl cellosolve acetate; ethyl cellosolve acetate; and butyl cellosolve acetate. Cellosolve esters, propylene glycol esters such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethers such as 1,2-dimethoxyethane, 1,2-diethoxyethane, tetrahydrofuran, anisole, methyl ethyl ketone, methyl isobutyl Ketones, ketones such as methyl-n-amyl ketone, cyclohexanone, isophorone, dimethylformamide, Methylacetamide, N- methylpyrrolidone, dimethyl sulfoxide, the solvent is selected from aprotic polar solvents such as sulfolane, or their composite solvents include.

The transmittance of the thin film obtained from the radiation-sensitive composition of the present invention at a wavelength of 157 nm is 100 nm.
In particular, a composition in which the content is 40% or more is preferably used. Further, those having a transmittance of 50% or more are more preferably used. The transmittance at a wavelength of 157 nm can be measured with a vacuum ultraviolet spectrophotometer after applying the radiation-sensitive composition onto a calcium fluoride substrate with a spin coater and heating the mixture at 90 ° C. for 2 minutes on a hot plate.

The radiation-sensitive composition of the present invention is applied on a substrate to be processed, dried, and usually used as a thin film having a thickness of 0.2 μm to 2 μm. This thin film is subjected to pattern exposure using radiation such as ultraviolet rays, far ultraviolet rays, vacuum ultraviolet rays, electron beams, and X-rays. In particular, it is suitably used for pattern exposure using vacuum ultraviolet rays. By heating after the exposure, the base generated at the time of the exposure, or a high molecular weight by the action of an acid,
The pattern formation becomes possible by making it less soluble than the unexposed portion. Heating after exposure is preferably performed in a temperature range of 50 ° C to 150 ° C for 30 seconds to 30 minutes.

The development of the radiation-sensitive composition of the present invention can be carried out using a known developer. Examples include inorganic alkalis such as hydroxides, carbonates, phosphates, silicates and borates of alkali metals, amines such as 2-diethylaminoethanol, monoethanolamine and diethanolamine, and tetramethylammonium hydroxide. And aqueous solutions containing one or more quaternary ammoniums such as choline and choline.

[0041]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

Example 1 3,3,3-trifluoropropyltrimethoxysilane
7 g, methyltrimethoxysilane 42.6 g, water 20.
3 g was reacted in methyl isobutyl ketone using phosphoric acid as a catalyst, and the solvent was distilled off to obtain a polymer. 5 g of the obtained polymer and 100 mg of benzoin tosylate were dissolved in 95 g of propylene glycol monomethyl ether to obtain a resist composition. 100 nm of a thin film obtained by casting this resist composition on a calcium fluoride substrate
Per unit was 45% at a wavelength of 157 nm. This resist composition was applied on a silicon wafer by a spin coater, and heated on a hot plate at 110 ° C. for 1 minute to obtain a resist film having a thickness of 200 nm. The film was irradiated with F2 excimer laser light through a mask, heated on a hot plate at 110 ° C. for 5 minutes, and developed with a 2.38% aqueous solution of tetramethylammonium hydroxide to obtain a fine pattern. At an exposure of 50 mJ, a pattern of 0.2 μm was obtained.

Example 2 Evaluation was performed in the same manner as in Example 1 except that [[(2-nitrobenzyl) oxy] carbonyl] hexylamine was used instead of benzoin tosylate. At an exposure of 50 mJ, a pattern of 0.2 μm was obtained.

Example 3 7.5 g of tridecafluoro-1,1,2,2-tetrahydrooctyltriethoxysilane, methyltrimethoxysilane 3
0.7 g, 9.9 g of phenyltrimethoxysilane, water 1
5.7 g was reacted in methyl isobutyl ketone using phosphoric acid as a catalyst, and the solvent was distilled off to obtain a polymer. 5 g of the obtained polymer, [[(2-nitrobenzyl) oxy]
Carbonyl] hexylamine (100 mg) was dissolved in propylene glycol monomethyl ether (95 g) to obtain a resist composition. The transmittance per 100 nm of a thin film obtained by casting this resist composition on a calcium fluoride substrate was 55% at a wavelength of 157 nm. Using this resist composition, coating was performed in the same manner as in Example 1,
Exposure and development were performed to obtain a fine pattern. At an exposure of 30 mJ, a pattern of 0.2 μm was obtained.

Example 4 3,3,3-trifluoropropyltrimethoxysilane
7 g, 21.3 g of methyltrimethoxysilane, 18.8 g of dimethyldimethoxysilane, and 17.4 g of water were reacted in methyl isobutyl ketone using phosphoric acid as a catalyst, and the solvent was distilled off to obtain a polymer. 5 g of the obtained polymer and 100 mg of benzoin tosylate were dissolved in 95 g of propylene glycol monomethyl ether to obtain a resist composition. The transmittance per 100 nm of a thin film obtained by casting this resist composition on a calcium fluoride substrate was 42% at a wavelength of 157 nm. Using this resist composition, a fine pattern was obtained in the same manner as in Example 1 except that development was performed with methyl isobutyl ketone instead of tetramethylammonium hydroxide. 60mJ
With a light exposure of 0.3 μm, a pattern of 0.3 μm was obtained.

Example 5 3,3,3-trifluoropropyltrimethoxysilane 2.7
g, methyl trimethoxysilane 42.6 g, water 17.6
g was reacted in methyl isobutyl ketone using phosphoric acid as a catalyst, and the solvent was distilled off to obtain a polymer. 5 g of the obtained polymer, triphenylsulfonium triflate 10
0 mg of propylene glycol monomethyl ether 95
g) to give a resist composition. The transmittance per 100 nm of a thin film obtained by casting this resist composition on a calcium fluoride substrate was 36% at a wavelength of 157 nm. Using this resist composition, coating, exposure and development were carried out in the same manner as in Example 1 to obtain a fine pattern. At an exposure of 80 mJ, a 0.2 μm pattern was obtained.

Comparative Example 1 42.6 g of methyltrimethoxysilane and 16.8 g of water were reacted in methyl isobutyl ketone using phosphoric acid as a catalyst, and the solvent was distilled off to obtain a polymer. 5 g of the obtained polymer and 100 mg of benzoin tosylate were dissolved in 95 g of propylene glycol monomethyl ether to obtain a resist composition. The transmittance per 100 nm of a thin film obtained by casting this resist composition on a calcium fluoride substrate was 30% at a wavelength of 157 nm. Using this resist composition, coating was performed in the same manner as in Example 1,
Exposure and development were performed to obtain a fine pattern. At an exposure of 150 mJ, a pattern of only 0.5 μm was obtained.

Comparative Example 2 Evaluation was performed in the same manner as in Comparative Example 1 except that [[(2-nitrobenzyl) oxy] carbonyl] hexylamine was used instead of benzoin tosylate. At an exposure of 150 mJ, a pattern of only 0.5 μm was obtained.

[0049]

As described above, the radiation-sensitive composition of the present invention provides a high-resolution and high-sensitivity composition by using a radiation-sensitive composition containing a siloxane polymer having a fluorine-containing substituent. It became possible to obtain.

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Claims (4)

[Claims] 1. A radiation-sensitive composition comprising a siloxane polymer having a fluorine-containing substituent and an acid generator which generates an acid upon irradiation with radiation. 2. A radiation-sensitive composition comprising a siloxane polymer having a fluorine-containing substituent and a base generator which generates a base upon irradiation with radiation. 3. The radiation-sensitive composition according to claim 1, wherein the transmittance of the thin film of the radiation-sensitive composition to light having a wavelength of 157 nm is 40% or more per 100 nm in film thickness. . 4. The radiation-sensitive composition according to claim 1, wherein the siloxane polymer is a silsesquioxane polymer.