JP2007154047A - Polysiloxane and radiation-sensitive resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a radiation-sensitive resin composition capable of remarkably decreasing development defects while keeping good properties of polysiloxane and sufficient principal resist performance as a chemical amplification resist and provide a polysiloxane useful as a constituent component of the radiation-sensitive resin composition. <P>SOLUTION: The invention provides a polysiloxane obtained by polycondensation of a silane compound expressed by general formula (I) and SiR<SP>4</SP><SB>3</SB>H (R<SP>1</SP>groups are each independently 1-20C alkoxy, 2-7C acyloxy or a halogen atom; R<SP>2</SP>is 1-20C bivalent hydrocarbon group which may have substituents; and R<SP>3</SP>is univalent acid-dissociable group) in the presence of water, and a radiation-sensitive resin composition containing the polysiloxane and a radiation-sensitive acid generator. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention comprises a polysiloxane having an acid-dissociable group and a silicon-hydrogen bond, and the radiation-sensitive material suitable for microfabrication using radiation such as deep ultraviolet rays, electron beams, and X-rays. The present invention relates to a functional resin composition.

In recent years, demands for higher density and higher integration of LSIs (highly integrated circuits) are increasing, and along with this, miniaturization of wiring patterns is also progressing rapidly. As one of the means that can cope with such miniaturization of the wiring pattern, there is a method of shortening the radiation used in the lithography process. In recent years, g-line (wavelength 436 nm), i-line (wavelength 365 nm), etc. Instead of ultraviolet rays, far ultraviolet rays such as KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm) and F ₂ excimer laser (wavelength 157 nm), electron beams, X-rays and the like are used.

  By the way, in the conventional resist composition, novolak resin, poly (vinylphenol) and the like have been used as a resin component, but these materials contain an aromatic ring in the structure and have strong absorption at a wavelength of 193 nm. For example, in a lithography process using an ArF excimer laser, high accuracy corresponding to high sensitivity, high resolution, high aspect ratio, etc. cannot be obtained.

Accordingly, there is a demand for a resist resin material having a dry etching resistance of 193 nm or less, particularly transparent to ArF excimer laser (wavelength 193 nm), F ₂ excimer laser (wavelength 157 nm), and the like and having a dry etching resistance equal to or higher than that of an aromatic ring It has been. One of them is a siloxane-based polymer, and MIT RRKunz et al. Presented a measurement result that a polysiloxane-based polymer has excellent transparency at a wavelength of 193 nm or less, particularly at 157 nm. It is reported that it is suitable for a resist material in a lithography process using a wavelength (see, for example, Non-Patent Document 1 and Non-Patent Document 2). In addition, it is also known that polysiloxane polymers are excellent in dry etching resistance, and among them, a resist containing polysilsesquioxane having a ladder structure has high plasma resistance.

On the other hand, a chemically amplified resist using a siloxane polymer has already been reported. For example, polysilylation with a silicon-hydrogen bond that is transparent to both ArF excimer laser (wavelength 193 nm) and F ₂ excimer laser (wavelength 157 nm), that is, hydrosilation to the main chain of hydrogensilsesquioxane. It is known that polysiloxane obtained by introducing a group having an acid dissociable group by reaction has lithographic characteristics suitable as a resist (for example, see Patent Document 1).

  However, since a metal catalyst is used in the above hydrosilylation reaction, the metal compound originating from the catalyst remains in the obtained polysiloxane, and accordingly, when the polysiloxane is used as a resist, There were problems such as numerous development defects.

J. Photopolym. Sci. Technol., Vol.12, No.4 (1999) P.561-570 SPIE, Vol. 3678 (1999) P.13-23 International pamphlet WO2005 / 007747

  Therefore, the object of the present invention is to provide a radiation sensitivity capable of significantly reducing development defects while maintaining good characteristics based on polysiloxane, sufficient basic performance as a resist and stability during storage as a chemically amplified resist. It is in providing the resin composition and polysiloxane useful as a structural component of the said radiation sensitive resin composition.

  In view of such circumstances, the present inventors have intensively studied a method for producing a polysiloxane having an acid-dissociable group and a silicon-hydrogen bond. The following general formula (I)

(In the formula, each R ¹ independently represents an alkoxyl group having 1 to 20 carbon atoms, an acyloxy group having 2 to 7 carbon atoms, or a halogen atom, and R ² may have a substituent. A good divalent hydrocarbon group having 1 to 20 carbon atoms, and R ³ represents a monovalent acid-dissociable group.

(Hereinafter, this may be abbreviated as “silane compound (I)”), and the following general formula (II)

(In formula, each R < ⁴ > shows a C1-C20 alkoxyl group, a C2-C7 acyloxy group, or a halogen atom each independently.)

The following general formula (III) is obtained by polycondensation of a silane compound represented by the formula (hereinafter sometimes abbreviated as “silane compound (II)”) in the presence of water.

（式中、Ｒ²、及びＲ³は前記定義のとおりである。）で表される構造単位（以下、これを「構造単位（ＩＩＩ）」と略記することがある。）、及び下記の式（ＩＶ）、

(Wherein R ² and R ³ are as defined above) (hereinafter, this may be abbreviated as “structural unit (III)”), and the following formula (IV),

(Hereinafter, this may be abbreviated as “structural unit (IV)”) (hereinafter, this may be abbreviated as “polysiloxane (A)”). By using the polysiloxane (A), it is possible to significantly reduce development defects while maintaining good characteristics based on polysiloxane and sufficient basic performance as a resist as a chemically amplified resist. The inventors have found that a functional resin composition can be obtained and have completed the present invention.

That is, the present invention
(1) A polysiloxane having a structural unit (III) and a structural unit (IV) obtained by polycondensation of a silane compound (I) and a silane compound (II) in the presence of water,
(2) A radiation-sensitive resin composition comprising the polysiloxane obtained in (1) above and a radiation-sensitive acid generator,
(3) Production method of polysiloxane having structural unit (III) and structural unit (IV) by polycondensation of silane compound (I) and silane compound (II) in the presence of water,
(4) The polysiloxane according to claim 1, wherein the metal content is 200 ppb or less, and
(5) A radiation-sensitive resin composition comprising the polysiloxane of (4) above and a radiation-sensitive acid generator,
Consists of.

  According to the present invention, it is possible to provide a radiation-sensitive resin composition capable of significantly reducing development defects while maintaining good characteristics based on polysiloxane and sufficient basic performance as a resist as a chemically amplified resist. Is possible. Therefore, the radiation-sensitive resin composition can be used particularly suitably for the production of LSIs that are expected to be increasingly miniaturized in the future. In addition, the polysiloxane (A) of the present invention can be used particularly suitably as a constituent component in the radiation sensitive resin composition.

Hereinafter, the present invention will be described in more detail.
Silane compound (I):
In the general formula (I), R ¹ represents a linear, branched, or cyclic alkyloxy group having 1 to 20 carbon atoms, such as a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, n-butoxy group, 2-methylpropoxy group, 1-methylpropoxy group, t-butoxy group, n-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group Group, n-dodecyloxy group, n-tetradecyloxy group, n-hexadecyloxy group, n-octadecyloxy group, eicosyloxy group, cyclopentyloxy group, cyclohexyloxy group and the like. Among these, a methoxy group, an ethoxy group, etc. are preferable.

Examples of the acyloxy group having 2 to 7 carbon atoms represented by R ¹ include an acyloxy group whose alkyl moiety is an alkyl group such as a methyl group, an ethyl group, and an n-propyl group. Among these, an acetoxy group and the like are preferable.

Examples of the halogen atom represented by R ¹ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, a chlorine atom is preferable.

Examples of the divalent hydrocarbon group having 1 to 20 carbon atoms represented by R ² include a methylene group, a 1,1-ethylene group, a 1,2-ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group. Linear or branched alkylene group such as methylene group; cyclobutane such as cyclopentyl group and cyclohexyl group, cyclopentane, cyclohexane, cycloheptane, cyclooctane, bicyclo [2.2.1] heptane, bicyclo [2.2. 2] Octane, tricyclo [5.2.1.0 ^2,6 ] decane, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] groups derived from alicyclic hydrocarbons such as dodecane and adamantane; groups derived from aromatic hydrocarbons such as benzene, toluene, ethylbenzene, i-propylbenzene and naphthalene.

  Examples of the substituent that the above divalent hydrocarbon group may have include, for example, an acid dissociable group that generates a carboxyl group, an alcoholic hydroxyl group, a phenolic hydroxyl group, or the like in the presence of an acid, as well as fluorine. Atom, hydroxyl group, carboxyl group, epoxy group, oxo group, amino group, cyano group, cyanyl group, isocyanyl group, (meth) acryloyl group, (meth) acryloyloxy group, group having lactonyl group, carboxylic anhydride group A group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, a hydroxyalkyl group having 1 to 4 carbon atoms, a cyanoalkyl group having 2 to 5 carbon atoms, and an alkoxyl group having 1 to 4 carbon atoms , An alkoxymethyl group having 2 to 5 carbon atoms, an alkoxycarbonyl group having 2 to 5 carbon atoms, an alkoxycarbonylamino group having 2 to 5 carbon atoms, and 1 to 4 carbon atoms Alkoxysulfonyl group, and the like alkylaminosulfonyl group having 1 to 4 carbon atoms. One or more or one or more of these substituents may be present in each substituted derivative.

In the general formula (I), R ² may be, for example, bicyclo [2.2.1] heptane, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] groups derived from dodecane or adamantane, groups obtained by substituting these groups with fluorine atoms, trifluoromethyl groups, etc., more specifically, the following formulas (i-1) to (i-4) ) (In each group, the silicon atom is bonded to the carbon atom constituting the norbornane ring located at the top of the formula), the group represented by the following formula (i-5), 1,2-ethylene group, trimethylene group and the like are preferable.

[In Formula (i-1)-Formula (i-4), each n is 0 or 1. ]

Examples of the monovalent acid-dissociable group represented by R ³ include groups represented by the following formulas (1-1) to (1-3), cyclic monovalent hydrocarbon groups having 3 to 20 carbon atoms, Examples thereof include a monovalent heterocyclic group having 6 to 25 atoms, a trialkylsilyl group (wherein each alkyl group has 1 to 6 carbon atoms), an oxoalkyl group having 4 to 20 carbon atoms, and the like.

[In Formula (1-1), each R < ⁵ > is mutually independently a C1-C4 linear or branched alkyl group, or C4-C20 monovalent alicyclic. A hydrocarbon group or a substituted derivative thereof, or any two R ⁵ 's bonded to each other, each of which is a divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms together with the carbon atoms to which they are bonded Or a substituted derivative thereof, and the remaining R ⁵ is a linear or branched alkyl group having 1 to 4 carbon atoms, or a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms, or A substituted derivative is shown. ]

[In the formula (1-2), R ⁶ represents a group represented by the above formula (1-1), a cyclic monovalent hydrocarbon group having 3 to 20 carbon atoms, or a monovalent complex having 6 to 25 atoms. A cyclic group, a trialkylsilyl group (provided that each alkyl group has 1 to 6 carbon atoms) or an oxoalkyl group having 4 to 20 carbon atoms, and a is an integer of 0 to 6. ]

[In the formula (1-3), each R ⁷ independently represents a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, or two R ⁷ are bonded to each other to form a ring, and R ⁸ is a linear, branched, or cyclic monovalent hydrocarbon group having 1 to 20 carbon atoms, or a monovalent hydrocarbon having 6 to 25 atoms. or showing a heterocyclic group, or one of R ⁷ and the R ⁸ are bonded to each other and form a ring, the alkyl group of R ^7, form two R ⁷ are bonded to each other The ring formed by bonding one of R ⁷ and R ⁸ to each other, the monovalent hydrocarbon group of R ^8, the monovalent heterocyclic group, and any one of R ⁷ and R ⁸ are each substituted. Also good. ]

In formula (1-1), examples of the linear or branched alkyl group having 1 to 4 carbon atoms of R ⁵ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n- A butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group and the like can be mentioned.

In addition, a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms represented by R ⁵ and any two R ⁵ 's bonded to each other to form a carbon atom having 4 to Examples of the divalent alicyclic hydrocarbon group of 20 include cycloalkanes such as cyclobutane, cyclopentane, cyclopentene, cyclohexane, cyclohexene, cycloheptane, and cyclooctane, or groups derived from cycloalkenes; 2.1] heptane, bicyclo [2.2.2] octane, tricyclo [5.2.1.0 ^2,6 ] decane, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] groups derived from alicyclic hydrocarbons such as dodecane and adamantane.

Moreover, as a substituent in the substituted derivative of the monovalent or divalent alicyclic hydrocarbon group, for example, the divalent hydrocarbon group of R ² in the general formula (I) may have. Examples include the same groups as those described for the substituent. One or more or one or more of these substituents may be present in each substituted derivative.

  Examples of the group represented by the formula (1-1) include a t-butyl group, a t-amyl group, a 2-ethyl-2-butyl group, a 3-methyl-3-pentyl group, and 1,1-diethylpropyl. 1 group such as 1-methylcyclopentyl group, 1-ethylcyclopentyl group, 1-n-propylcyclopentyl group, 1-methylcyclohexyl group, 1-ethylcyclohexyl group, 1-n-propylcyclohexyl group, etc. An alkylcycloalkyl group;

  2-methylbicyclo [2.2.1] heptan-2-yl group, 2-methyl-5-hydroxybicyclo [2.2.1] heptan-2-yl group, 2-methyl-6-hydroxybicyclo [2] 2.1] heptane-2-yl group, 2-methyl-5-cyanobicyclo [2.2.1] heptan-2-yl group, 2-methyl-6-cyanobicyclo [2.2.1] heptane 2-yl group, 2-ethylbicyclo [2.2.1] heptan-2-yl group, 2-ethyl-5-hydroxybicyclo [2.2.1] heptan-2-yl group, 2-ethyl- 6-hydroxybicyclo [2.2.1] heptan-2-yl group,

8-methyltricyclo [5.2.1.0 ^2,6 ] decan-8-yl group, 8-methyl-4-hydroxytricyclo [5.2.1.0 ^2,6 ] decan-8-yl Group, 8-methyl-4-cyanotricyclo [5.2.1.0 ^2,6 ] decan-8-yl group, 8-ethyltricyclo [5.2.1.0 ^2,6 ] decane-8. -Yl group, 8-ethyl-4-hydroxytricyclo [5.2.1.0 ^2,6 ] decan-8-yl group,

4-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodecan-4-yl group, 4-methyl-9-hydroxytetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodecan-4-yl group, 4-methyl-10-hydroxytetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodecan-4-yl group, 4-methyl-9-cyanotetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodecan-4-yl group, 4-methyl-10-cyanotetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodecan-4-yl group, 4-ethyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodecan-4-yl group, 4-ethyl-9-hydroxytetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodecan-4-yl group, 4-ethyl-10-hydroxytetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodecan-4-yl group,

  2-methyladamantan-2-yl group, 2-methyl-3-hydroxyadamantan-2-yl group, 2-ethyladamantan-2-yl group, 2-ethyl-3-hydroxyadamantan-2-yl group, 2- n-propyladamantan-2-yl group, 2-n-butyladamantan-2-yl group, 2-methoxymethyladamantan-2-yl group, 2-methoxymethyl-3-hydroxyadamantan-2-yl group, 2- An alicyclic hydrocarbon group substituted with an alkyl group such as an ethoxymethyladamantan-2-yl group and a 2-n-propoxymethyladamantan-2-yl group;

1-methyl-1-cyclopentylethyl group, 1-methyl-1- (2-hydroxycyclopentyl) ethyl group, 1-methyl-1- (3-hydroxycyclopentyl) ethyl group, 1-methyl-1-cyclohexylethyl group, 1-methyl-1- (3-hydroxycyclohexyl) ethyl group, 1-methyl-1- (4-hydroxycyclohexyl) ethyl group, 1-methyl-1-cycloheptylethyl group, 1-methyl-1- (3- Hydroxycycloheptyl) ethyl group, 1-methyl-1- (4-hydroxycycloheptyl) ethyl group, 1-methyl-1- (bicyclo [2.2.1] heptan-2-yl) ethyl group, 1 -Methyl-1- (5-hydroxybicyclo [2.2.1] heptan-2-yl) ethyl group, 1-methyl-1- (6-hydroxybicyclo [2 2.1] heptan-2-yl) ethyl group, 1-methyl-1- (tetracyclo [6.2.1.1 ^3,6 .0 ^2,7] dodecane-4-yl) ethyl group, 1-methyl -1- (9-hydroxy tetracyclo [6.2.1.1 ^3,6 .0 ^2,7] dodecane-4-yl) ethyl group, 1-methyl-1- (10-hydroxy-tetracyclo [6. 2.1.1 ^3,6 .0 ^2,7 ] dodecan-4-yl) ethyl group, 1-methyl-1- (tricyclo [5.2.1.0 ^2,6 ] decan-8-yl) ethyl Group, 1-methyl-1- (4-hydroxytricyclo [5.2.1.0 ^2,6 ] decan-8-yl) ethyl group, 1-methyl-1- (adamantan-1-yl) ethyl group 1-methyl-1- (3-hydroxyadamantan-1-yl) ethyl group, 1,1-dicyclopentylethyl group, 1,1-di 2-hydroxycyclopentyl) ethyl group, an ethyl group having a 1,1-di (3-hydroxycyclopentyl) ethyl alicyclic hydrocarbon group substituted with an alkyl group such as a group;

1,1-dicyclohexylethyl group, 1,1-di (3-hydroxycyclohexyl) ethyl group, 1,1-di (4-hydroxycyclohexyl) ethyl group, 1,1-dicycloheptylethyl group, 1,1-di (3-hydroxycycloheptyl) ethyl group, 1,1-di (4-hydroxycycloheptyl) ethyl group, 1,1-di (bicyclo [2.2.1] heptan-2-yl) ethyl group, 1,1-di (5-hydroxybicyclo [2.2.1] heptan-2-yl) ethyl group, 1,1-di (6-hydroxybicyclo [2.2.1] heptan-2-yl) ethyl Group, 1,1-di (tetracyclo [6.2.1.1 ^3,6 .0 ^2,7 ] dodecan-4-yl) ethyl group, 1,1-di (9-hydroxytetracyclo [6.2 .1.1 ^3,6 .0 ^2,7] dodecane-4-yl) Butyl group, 1,1-di (10-hydroxy-tetracyclo [6.2.1.1 ^3,6 .0 ^2,7] dodecane-4-yl) ethyl group, 1,1-di (tricyclo [5. 2.1.0 ^2,6 ] decan-8-yl) ethyl group, 1,1-di (4-hydroxytricyclo [5.2.1.0 ^2,6 ] decan-8-yl) ethyl group, Ethyl group having an alicyclic hydrocarbon group substituted with a hydroxyl group such as 1,1-di (adamantan-1-yl) ethyl group, 1,1-di (3-hydroxyadamantan-1-yl) ethyl group, etc. Is mentioned.

In the formula (1-2), examples of the cyclic monovalent hydrocarbon group having 3 to 20 carbon atoms represented by R ⁶ include a cyclobutyl group, a cyclopentyl group, a cyclopentenyl group, a cyclohexyl group, a cyclohexenyl group, and a cycloheptyl group. Group, cyclooctyl group, bicyclo [2.2.1] heptan-2-yl group, bicyclo [2.2.2] octane, tricyclo [5.2.1.0 ^2,6 ] decan-3-yl group , Tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodecan-4-yl group, adamantane-1-yl group and the like.

Examples of the monovalent heterocyclic group having 6 to 25 atoms represented by R ⁶ include 2-tetrahydrofuranyl group and 2-tetrahydropyranyl group.

Examples of the trialkylsilyl group represented by R ⁶ include trimethylsilyl group, ethyldimethylsilyl group, methyldiethylsilyl group, triethylsilyl group, i-propyldimethylsilyl group, methyldii-propylsilyl group, tri-i- Examples thereof include a propylsilyl group and a t-butyldimethylsilyl group.

Examples of the oxoalkyl group having 4 to 20 carbon atoms represented by R ⁶ include a 3-oxocyclopentyl group, a 3-oxocyclohexyl group, a 4-oxocyclohexyl group, and a 4-methyl-2-oxooxane-4-yl group. , 5-methyl-2-oxooxolan-5-yl group and the like.

  Examples of the group represented by the formula (1-2) include a t-butoxycarbonyl group, a t-amyloxycarbonyl group, a 1,1-diethylpropoxycarbonyl group, a 1-methylcyclopentyloxycarbonyl group, and 1-ethylcyclopentyl. Oxycarbonyl group, 1-methylcyclohexyloxycarbonyl group, 1-ethylcyclohexyloxycarbonyl group, 1-methyl-2-cyclopentenyloxycarbonyl group, 1-ethyl-2-cyclopentenyloxycarbonyl group, (2-methylbicyclo [ 2.2.1] heptan-2-yl) oxycarbonyl group, (2-ethylbicyclo [2.2.1] heptan-2-yl) oxycarbonyl group, (2-methyladamantan-2-yl) oxycarbonyl Group, (2-ethyladamantan-2-yl) oxyca Boniru group,

  t-butoxycarbonylmethyl group, t-amyloxycarbonylmethyl group, 1,1-diethylpropoxycarbonylmethyl group, 1-methylcyclopentyloxycarbonylmethyl group, 1-ethylcyclopentyloxycarbonylmethyl group, 1-methylcyclohexyloxycarbonylmethyl Group, 1-ethylcyclohexyloxycarbonylmethyl group, 1-methyl-2-cyclopentenyloxycarbonylmethyl group, 1-ethyl-2-cyclopentenyloxycarbonylmethyl group, (2-methylbicyclo [2.2.1] heptane -2-yl) oxycarbonylmethyl group, (2-ethylbicyclo [2.2.1] heptan-2-yl) oxycarbonylmethyl group, (2-methyladamantan-2-yl) oxycarbonylmethyl group, (2 -Ethyla Kalimantan 2-yl) oxycarbonyl methyl group, 2-tetrahydrofuranyl butyloxycarbonylmethyl group, 2-tetrahydropyranyloxy carbonyl methyl group,

  1-methoxyethoxycarbonylmethyl group, 1-ethoxyethoxycarbonylmethyl group, (1-methyl-1-cyclopentylethoxy) carbonylmethyl group, (1-methyl-1-cyclohexylethoxy) carbonylmethyl group, [1-methyl-1 -(Bicyclo [2.2.1] heptan-2-yl) ethoxy] carbonylmethyl group, [1-methyl-1- (adamantan-1-yl) ethoxy] carbonylmethyl group, 2-tetrahydrofuranyloxycarbonylmethyl group , 2-tetrahydropyranyloxycarbonylmethyl group and the like.

In formula (1-3), examples of the linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms represented by R ⁷ include a methyl group, an ethyl group, an n-propyl group, and an i-propyl group. N-butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group, n-pentyl group, neopentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group , N-nonyl group, n-decyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group and the like.

Examples of the ring formed by bonding two R ⁷ to each other include a 3- to 8-membered ring formed together with the carbon atom to which two R ⁷ are bonded.

Examples of the linear, branched or cyclic monovalent hydrocarbon group having 1 to 20 carbon atoms represented by R ⁸ include, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n -Butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group, n-pentyl group, neopentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n -Linear or branched alkyl groups such as nonyl group and n-decyl group; cycloalkyl groups such as cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group and cyclooctyl group;

A bicyclo [2.2.1] heptan-2-yl group, a bicyclo [2.2.2] octan-2-yl group, a tricyclo [5.2.1.0 ^2,6 ] decan-3-yl group, Tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] groups derived from alicyclic hydrocarbons such as dodecan-4-yl group, adamantane-1-yl group, adamantane-2-yl group, etc .; phenyl group, o-tolyl group, m-tolyl group Aryl groups such as p-tolyl group, 1-naphthyl group and 2-naphthyl group; aralkyl groups such as benzyl group, α-methylbenzyl group, α, α-dimethylbenzyl group and phenethyl group.

Examples of the monovalent heterocyclic group having 6 to 25 atoms represented by R ⁸ include oxetane, thietane, tetrahydrofuran, tetrahydrothiofuran, tetrahydropyran, tetrahydrothiopyran, and the following formula (1-3-1) Group derived from a heterocyclic compound such as a compound represented by (1-3-4).

The ring formed by bonding any one of R ⁷ and R ⁸ is, for example, 3 formed with the carbon atom to which R ⁷ is bonded and the oxygen atom to which R ⁸ is bonded. -8 membered ring etc. are mentioned.

The alkyl group represented by R ^{7, the} ring formed by bonding two R ^{7 s} to each other, the monovalent hydrocarbon group and monovalent heterocyclic group represented by R ⁸ , and any one R Examples of the substituent for the ring formed by bonding ⁷ and R ⁸ to each other include the substituent that the divalent hydrocarbon group represented by R ² in the general formula (I) may have. Examples thereof include the same groups as those shown. One or more or one or more of these substituents may be present in each substituted derivative.

In formula (1-3), preferred specific examples of the substituted monovalent hydrocarbon group represented by R ⁸ and the substituted monovalent heterocyclic group include a 4-hydroxy-n-butyl group, 6 -Hydroxy-n-hexyl group, 2-n-butoxyethyl group, 2- (2-hydroxyethoxy) ethyl group, (4-hydroxymethylcyclohexyl) methyl group, the following formulas (1-3-5) to (1- And the group represented by 3-8).

Examples of the group represented by the formula (1-3) include a methoxymethyl group, an ethoxymethyl group, an n-propoxymethyl group, an i-propoxymethyl group, an n-butoxymethyl group, a t-butoxymethyl group, and cyclopentyloxy. Substituted methyl groups such as methyl group, cyclohexyloxymethyl group, phenoxymethyl group, benzyloxymethyl group, phenethyloxymethyl group;
1-methoxyethyl group, 1-ethoxyethyl group, 1-n-propoxyethyl group, 1-i-propoxyethyl group, 1-n-butoxyethyl group, 1-t-butoxyethyl group, 1-cyclopentyloxyethyl group 1-cyclohexyloxyethyl group, 1-phenoxyethyl group, 1-benzyloxyethyl group, 1-phenethyloxyethyl group, 1-methyl-1-methoxyethyl group, 1-methyl-1-ethoxyethyl group, 1- Methyl-1-n-propoxyethyl group, 1-methyl-1-i-propoxyethyl group, 1-methyl-1-n-butoxyethyl group, 1-methyl-1-t-butoxyethyl group, 1-methyl- 1-cyclopentyloxyethyl group, 1-methyl-1-cyclohexyloxyethyl group, 1-methyl-1-phenoxyethyl group, 1-methyl- -Benzyloxyethyl group, 1-methyl-1-phenethyloxyethyl group, 1-methoxy-n-propyl group, 1-ethoxy-n-propyl group, 1-n-propoxy-n-propyl group, 1-phenoxy- 1-substituted n-propyl group such as n-propyl group, 2-methoxy-n-propyl group, 2-ethoxy-n-propyl group, 2-n-propoxy-n-propyl group, 2-phenoxy-n- 2-substituted-n-propyl group such as propyl group, 1-methoxy-n-butyl group, 1-ethoxy-n-butyl group, 1-n-propoxy-n-butyl group, 1-phenoxy-n-butyl group Alkyl groups having a substituent such as: tetrahydrofuran-2-yl group, 2-methyltetrahydrofuran-2-yl group, tetrahydropyran-2-yl group, 2-methyltetrahydropyran- - heterocyclic group such as-yl group.

  Specific examples of the silane compound (I) include, for example, silane compounds described in JP-A Nos. 2002-105086 and 2002-128788.

Silane compound (II):
In the general formula (II), examples of the alkoxy group having 1 to 20 carbon atoms, the acyloxy group having 2 to 7 carbon atoms, and the halogen atom represented by R ⁴ include carbon represented by R ¹ in the general formula (I). The thing similar to what was shown about the C1-C20 alkoxyl group, the C2-C7 acyloxy group, a halogen atom, etc. are mentioned.

Other condensable silane compounds:
The polysiloxane (A) of the present invention may have other structural units as long as the gist of the present invention is not impaired. For example, the following general formula (V)

(In the formula, R ′ represents an optionally substituted divalent hydrocarbon group having 1 to 20 carbon atoms, and R ″ represents an alkoxyl group, cyano group, or hydroxyl group having 1 to 20 carbon atoms. .)

And a structural unit represented by In the general formula (V), examples of the divalent hydrocarbon group having 1 to 20 carbon atoms that may have a substituent represented by R ′ include, for example, the divalent R ² in the general formula (I). And the same groups as those shown for the hydrocarbon group. As the alkoxyl group having 1 to 20 carbon atoms represented by R ", for example, such as the same groups as those indicated for alkoxyl group having 1 to 20 carbon atoms represented by R ¹ in the general formula (I) may be mentioned One or more structural units (V) may be present in the polysiloxane (A).

  The polysiloxane (A) having the structural unit (V) is, for example, a condensable silane compound corresponding to the structural unit (V) (hereinafter sometimes abbreviated as “silane compound V”) and a silane compound. It can be produced by a method of polycondensation with (I) and the silane compound (II).

Polysiloxane (A):
In the polysiloxane (A), the content of the structural unit (III) is usually more than 5 mol% and 80 mol% or less, preferably 5 to 70 mol%, particularly preferably 10 to 70, based on all structural units. Mol%. In this case, if the content of the structural unit (III) is 5 mol% or less, the resolution tends to be lowered as a resist. On the other hand, if it exceeds 80 mol%, the pattern shape may be impaired as a resist. . The content of the structural unit (IV) in the polysiloxane (A) is usually more than 15 mol% and 70 mol% or less, preferably 20 to 70 mol%, particularly preferably 20 to 60 mol%.

  The metal content in the polysiloxane (A) is preferably 50 ppb or less, more preferably 20 ppb or less, and even more preferably 10 ppb or less.

  The polysiloxane (A) is intramolecularly cross-linked and / or intermolecularly cross-linked by one or more of acid dissociable bonding groups represented by the following general formula (2-1) or general formula (2-2). It may be.

[In General Formula (2-1) and General Formula (2-2), each R ¹³ is independently of each other a hydrogen atom or a linear, branched, or cyclic group having 1 to 8 carbon atoms. Two R ^{13 s} representing an alkyl group or bonded to the same carbon atom are bonded to each other to form a 3- to 8-membered carbocycle, and each R ¹⁴ is independently of each other; A methylene group or a linear, branched or cyclic alkylene group having 2 to 10 carbon atoms, wherein each b is independently of each other an integer of 0 to 10, and each c is independently of each other And each R ¹⁵ is independently of each other a (c + 1) -valent linear or branched saturated hydrocarbon group having 1 to 50 carbon atoms, 3 to 50 carbon atoms. (C + 1) -valent cyclic saturated hydrocarbon group, (c + 1) -valent aromatic hydrocarbon having 6 to 50 carbon atoms Or a (c + 1) -valent heterocyclic group having 6 to 50 atoms, the linear or branched saturated hydrocarbon group, cyclic saturated hydrocarbon group, aromatic hydrocarbon group, and heterocyclic ring In each of the formula groups, a hetero atom may be present in the main chain and / or side chain, and at least a part of the hydrogen atoms bonded to the carbon atoms are fluorine atoms, hydroxyl groups, carboxyl groups, or acyl groups. Each U ¹ independently represents —COO—, —NHCOO—, or NHCONH— (wherein —COO— and NHCOO— represent two bonds ( Any of-) may be bonded to R ¹⁴ or R ¹⁵ . ]

  Specific preferred examples of the acid dissociable linking group include groups represented by the following formulas (2-1-1) to (2-1-8).

  The weight average molecular weight in terms of polystyrene (hereinafter, this may be abbreviated as “Mw”) by gel permeation chromatography (GPC) of the polysiloxane (A) is 500 to 1,000,000, preferably 500 to 100,000, particularly preferably 500 to 40,000. In this case, if the Mw of the polysiloxane (A) is less than 500, the glass transition point of the resin tends to decrease, whereas if it exceeds 1,000,000, the solubility of the resin in the solvent tends to decrease. It is not preferable.

Production method of polysiloxane (A):
Polysiloxane (A) is produced by polycondensing silane compound (I) and silane compound (II) in the presence of water. The polycondensation method is not particularly limited as long as it does not adversely affect the production of polysiloxane (A), and a method generally used in polycondensation of condensable silane compounds can be applied. Examples include a method of reacting compound (I), silane compound (II), and, if necessary, silane compound (V) in the presence of a catalyst without solvent or in a solvent. The reaction temperature for polycondensation is usually −50 to 300 ° C., preferably 20 to 100 ° C., and the reaction time is usually about 1 minute to 100 hours.

  The polysiloxane (A) can be obtained by subjecting the reaction mixture obtained by the above method to a method generally used in the isolation and purification of organic compounds. For example, the polysiloxane (A) can be isolated by washing the reaction mixture with water and separating the solvent of the organic layer obtained by liquid separation under reduced pressure. In addition, after distilling off the solvent of said organic layer under pressure reduction, the solution of the predetermined density | concentration obtained by adding a suitable solvent in polysiloxane (A) is used as the raw material of the photosensitive resin composition of this invention as it is. It may be used as

  The catalyst is not particularly limited as long as it does not adversely affect the production of polysiloxane (A), and examples thereof include acid catalysts and basic catalysts that are generally used in the condensation reaction of condensable silane compounds. Of these, acidic catalysts are preferred. Examples of the acidic catalyst include hydrochloric acid, sulfuric acid, nitric acid, formic acid, acetic acid, n-propionic acid, butyric acid, valeric acid, oxalic acid, malonic acid, succinic acid, maleic acid, and fumaric acid. , Adipic acid, phthalic acid, terephthalic acid, acetic anhydride, maleic anhydride, citric acid, boric acid, phosphoric acid, titanium tetrachloride, zinc chloride, aluminum chloride, benzenesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, etc. Is mentioned. Among these, from the viewpoint of preventing the metal compound from remaining in the resulting polysiloxane (A), it is preferable to avoid the use of a metal catalyst. Hydrochloric acid, sulfuric acid, acetic acid, oxalic acid, malonic acid, maleic acid Fumaric acid, acetic anhydride, maleic anhydride and the like are preferably used. These acidic catalysts may be used alone or in admixture of two or more. The usage-amount of an acidic catalyst is 0.01-10,000 mass parts normally with respect to 100 mass parts of whole quantity of silane compound (I) and silane compound (II).

  The solvent used for polycondensation is not particularly limited as long as it does not adversely affect the production of polysiloxane (A). For example, 2-butanone, 2-pentanone, 3-methyl-2-butanone, 2- Linear or branched ketones such as hexanone, 4-methyl-2-pentanone, 3-methyl-2-pentanone, 3,3-dimethyl-2-butanone, 2-heptanone, 2-octanone; cyclopentanone Cyclic ketones such as 3-methylcyclopentanone, cyclohexanone, 2-methylcyclohexanone, 2,6-dimethylcyclohexanone, isophorone; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether Acetate, propylene glycol Propylene glycol monoalkyl ethers such as rumono-i-propyl ether acetate, propylene glycol mono-n-butyl ether acetate, propylene glycol mono-i-butyl ether acetate, propylene glycol mono-sec-butyl ether acetate, propylene glycol mono-t-butyl ether acetate acetate;

  Methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, n-propyl 2-hydroxypropionate, i-propyl 2-hydroxypropionate, n-butyl 2-hydroxypropionate, i-butyl 2-hydroxypropionate, Alkyl 2-hydroxypropionates such as sec-butyl 2-hydroxypropionate and t-butyl 2-hydroxypropionate; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy Alkyl 3-alkoxypropionates such as ethyl propionate; ethanol, n-propanol, i-propanol, n-butanol, t-butanol, cyclohexanol, ethylene glycol monomethyl ether, ethylene glycol Ethyl ether, ethylene glycol mono -n- propyl ether, ethylene glycol monobutyl -n- butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, alcohols such as propylene glycol monomethyl -n- propyl ether;

  Dialkylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol di-n-propyl ether, diethylene glycol di-n-butyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether Ethylene glycol monoalkyl ether acetates such as acetate; aromatic hydrocarbons such as toluene and xylene; ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, 3 -Methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3- Other esters such as toxibutyl propionate, 3-methyl-3-methoxybutyl butyrate, ethyl acetate, n-propyl acetate, n-butyl acetate, methyl acetoacetate, ethyl acetoacetate, methyl pyruvate, ethyl pyruvate And

  N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, benzyl ethyl ether, di-n-hexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, caproic acid, caprylic acid, 1-octanol, 1 -Nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate and the like.

  These solvents may be used alone or in admixture of two or more. The usage-amount of a solvent is 2,000 mass parts or less normally with respect to 100 mass parts of whole quantity of silane compound (I) and silane compound (II).

  In addition, during polycondensation, water is added to the reaction system. In this case, the amount of water added is usually 10,000 parts by mass or less with respect to 100 parts by mass of the total amount of the condensable silane compound to be used.

  In addition, about the manufacturing method of polysiloxane, it describes also in Unexamined-Japanese-Patent No. 2002-268225, Unexamined-Japanese-Patent No. 2002-268226, and Unexamined-Japanese-Patent No. 2002-268227, for example.

Radiation sensitive resin composition:
The radiation sensitive resin composition of the present invention contains a polysiloxane (A) and a radiation sensitive acid generator. In the radiation sensitive resin composition of the present invention, the polysiloxane (A) may be used alone or in admixture of two or more.

  Moreover, in this invention, 1 or more types of other polysiloxane can also be used together with polysiloxane (A). The other polysiloxane is not particularly limited. For example, in addition to a polysiloxane having no acid dissociable group, a structural unit derived from a bifunctional or tetrafunctional silane compound with respect to a condensation reaction. And polysiloxane having at least one structural unit selected from the group consisting of:

Radiation sensitive acid generator:
The radiation-sensitive acid generator in the present invention (hereinafter sometimes abbreviated as “acid generator”) is a component that generates an acid by exposure to radiation, and polysiloxane ( The acid dissociable groups present in A) are dissociated. As a result, the exposed portion of the resist film becomes readily soluble in an alkali developer, and has a function of forming a positive resist pattern. The acid generator is not particularly limited as long as it has the above-mentioned action. Preferred acid generators include compounds that generate sulfonic acid or carboxylic acid upon exposure (hereinafter referred to as “acid generator (B ) "May be abbreviated as") ".

  Examples of the sulfonic acid or carboxylic acid generated from the acid generator (B) include those described in JP-A No. 2002-220471, and more specifically, methyl group, ethyl group, n -Propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, tri Fluoromethyl group, pentafluoroethyl group, heptafluoro-n-propyl group, heptafluoro-i-propyl group, nonafluoro-n-butyl group, nonafluoro-i-butyl group, nonafluoro-sec-butyl group, nonafluoro-t- Butyl group, perfluoro-n-pentyl group, perfluoro-n-hexyl group, perfluoro-n-heptyl group, perfluoro-n-octyl , Norbornane, Jinoruborunan, adamantane, or a group or derived from camphor, sulfonic acids having a substituent derivative of these groups, or carboxylic acid.

  Examples of the acid generator (B) include an onium salt compound that generates the sulfonic acid or carboxylic acid, a sulfone compound that generates the sulfonic acid, a sulfonic acid compound that generates the sulfonic acid, and the sulfonic acid. Examples thereof include oxime compounds, carboxylic acid compounds that generate carboxylic acids, sulfonic acids, diazo ketone compounds that generate carboxylic acids, halogen-containing compounds that generate sulfonic acids or carboxylic acids, and the like.

  Examples of the onium salt compound include iodonium salts, sulfonium salts (including tetrahydrothiophenium salts), and more specifically, diphenyliodonium salts, dinaphthyliodonium salts, triphenylsulfonium salts. , Trinaphthylsulfonium salt, diphenyl / methylsulfonium salt, dicyclohexyl / 2-oxocyclohexylsulfonium salt, 2-oxocyclohexyldimethylsulfonium salt, phenyl / benzyl / methylsulfonium salt, 1-naphthyldimethylsulfonium salt, 1-naphthyldiethylsulfonium salt 1- (naphthalen-1-yl) tetrahydrothiophenium salt and one or more substituents such as hydroxyl group, alkyl group, alkoxyl group, cyano group, nitro group, and the like, Rui include derivatives substituted with one or more.

  Examples of the sulfone compounds include β-ketosulfones, β-sulfonylsulfones, and α-diazo compounds of these compounds. Examples of the sulfonic acid compounds include sulfonate esters, sulfones, and the like. Acid imides, aryl sulfonic acid esters, imino sulfonates, and the like. Examples of the oxime compound include aryl group-containing oxime sulfonic acids. Examples of the carboxylic acid compound include carboxylic acid compounds. Acid esters, carboxylic acid imides, carboxylic acid cyanates, and the like. Examples of the diazo ketone compounds include 1,3-diketo-2-diazo compounds, diazobenzoquinone compounds, diazonaphthoquinone compounds, and the like. The above halogen The organic compounds, such as haloalkyl group-containing hydrocarbon compounds, haloalkyl group-containing heterocyclic compounds, and the like.

  In this invention, an acid generator may be used individually or in mixture of 2 or more types, and may use together 2 or more types of the acid generator (B) which generate | occur | produces a different sulfonic acid. Two or more acid generators (B) that generate different carboxylic acids may be used in combination, or one or more acid generators (B) that generate sulfonic acids and acid generators that generate carboxylic acids ( One or more of B) may be used in combination.

  The amount of the acid generator used is usually 0.1 to 30 parts by mass, preferably 0.5 to 20 parts by mass with respect to 100 parts by mass of the total polysiloxane, from the viewpoint of ensuring sensitivity as a resist and developability. Part. In this case, if the amount of the acid generator used is less than 0.1 parts by mass, the sensitivity and developability of the resist tend to decrease. On the other hand, if it exceeds 30 parts by mass, the transparency to the radiation decreases as the resist. However, it tends to be difficult to obtain a rectangular resist pattern.

Additive:
Various additives such as an acid diffusion controller, a dissolution controller, a surfactant, and a storage stabilizer can be added to the radiation-sensitive resin composition of the present invention. The acid diffusion controller is a component having an action of controlling a diffusion phenomenon in a resist film of an acid generated from an acid generator by exposure and suppressing an undesirable chemical reaction in a non-exposed region. By blending such an acid diffusion control agent, the storage stability of the resulting radiation-sensitive resin composition is further improved, the resolution as a resist is further improved, and the holding time from exposure to development processing A change in the line width of the resist pattern due to fluctuations in (PED) can be suppressed, and a composition having excellent process stability can be obtained. The acid diffusion controller is preferably a nitrogen-containing organic compound whose basicity does not change by exposure or heat treatment in the resist pattern formation step. For example, a compound represented by the following general formula (3) (hereinafter referred to as “ The acid diffusion control agent (C) ”).

[In the general formula (3), each R ¹⁶ independently represents a hydrogen atom, a linear, branched, or cyclic alkyl group, an aryl group, or an aralkyl group. The group and the aralkyl group may be substituted with a functional group such as a hydroxyl group, U ² represents a divalent organic group, and s is an integer of 0 to 2. ]

  In the acid diffusion controller (C), hereinafter, a compound with s = 0 is abbreviated as “nitrogen-containing compound (C1)”, and a compound with s = 1 or 2 is abbreviated as “nitrogen-containing compound (C2)”. A polyamino compound having 3 or more nitrogen atoms and a polymer are collectively abbreviated as “nitrogen-containing compound (C3)”. Furthermore, examples of the nitrogen-containing organic compound other than the acid diffusion controller (C) include a quaternary ammonium hydroxide compound, an amide group-containing compound, a urea compound, and a nitrogen-containing heterocyclic compound.

  Examples of the nitrogen-containing compound (C1) include mono- (cyclo) alkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, cyclohexylamine; di-n-butylamine Di-n-pentylamine, di-n-hexylamine, di-n-heptylamine, di-n-octylamine, di-n-nonylamine, di-n-decylamine, cyclohexylmethylamine, dicyclohexylamine, etc. (Cyclo) alkylamine; triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, tri -N-nonylamine, tri-n-decylamine, cyclohexyl Tri (cyclo) alkylamines such as methylamine, dicyclohexylmethylamine and tricyclohexylamine; alkanolamines such as ethanolamine, diethanolamine and triethanolamine; aniline, N-methylaniline, N, N-dimethylaniline and 2-methylaniline , Aromatic amines such as 3-methylaniline, 4-methylaniline, 4-nitroaniline, 2,6-dimethylaniline, 2,6-diisopropylaniline, diphenylamine, triphenylamine and naphthylamine.

  Examples of the nitrogen-containing compound (C2) include ethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetrakis (2-hydroxypropyl) ethylenediamine, tetramethylenediamine, 1,3-bis [1- (4-aminophenyl) -1-methylethyl] benzenetetramethylenediamine, hexamethylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 4,4′- Diaminobenzophenone, 4,4′-diaminodiphenylamine, 2,2-bis (4-aminophenyl) propane, 2- (3-aminophenyl) -2- (4-aminophenyl) propane, 2- (4-aminophenyl) ) -2- (3-hydroxyphenyl) propane, 2- (4-aminophenyl) 2- (4-hydroxyphenyl) propane, 1,4-bis [1- (4-aminophenyl) -1-methylethyl] benzene, 1,3-bis [1- (4-aminophenyl) -1-methyl Ethyl] benzene, bis (2-dimethylaminoethyl) ether, bis (2-diethylaminoethyl) ether and the like.

  Examples of the nitrogen-containing compound (C3) include polyethyleneimine, polyallylamine, 2-dimethylaminoethylacrylamide polymer, and the like. Examples of the quaternary ammonium hydroxide compound include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-propylammonium hydroxide, tetra-n-butylammonium hydroxide, and the like.

  Examples of the amide group-containing compound include Nt-butoxycarbonyldi-n-octylamine, Nt-butoxycarbonyldi-n-nonylamine, Nt-butoxycarbonyldi-n-decylamine, and Nt. -Butoxycarbonyldicyclohexylamine, Nt-butoxycarbonyl-1-adamantylamine, Nt-butoxycarbonyl-N-methyl-1-adamantylamine, N, N-di-t-butoxycarbonyl-1-adamantylamine, N, N-di-t-butoxycarbonyl-N-methyl-1-adamantylamine, Nt-butoxycarbonyl-4,4′-diaminodiphenylmethane, N, N′-di-t-butoxycarbonylhexamethylenediamine, N, N, N ′, N′-tetra-t-butoxycarbonylhexame Range amine, N, N′-di-t-butoxycarbonyl-1,7-diaminoheptane, N, N′-di-t-butoxycarbonyl-1,8-diaminooctane, N, N′-di-t- Butoxycarbonyl-1,9-diaminononane, N, N′-di-t-butoxycarbonyl-1,10-diaminodecane, N, N′-di-t-butoxycarbonyl-1,12-diaminododecane, N, N '-Di-t-butoxycarbonyl-4,4'-diaminodiphenylmethane, Nt-butoxycarbonylbenzimidazole, Nt-butoxycarbonyl-2-methylbenzimidazole, Nt-butoxycarbonyl-2-phenylbenz In addition to Nt-butoxycarbonyl group-containing amino compounds such as imidazole, formamide, N-methylformamide, , N- dimethylformamide, acetamide, N- methylacetamide, N, N- dimethylacetamide, propionamide, benzamide, pyrrolidone, N- methylpyrrolidone and the like.

  Examples of the urea compound include urea, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, and tri-n-butyl. Examples include thiourea. Examples of the nitrogen-containing heterocyclic compound include imidazoles such as imidazole, 4-methylimidazole, 1-benzyl-2-methylimidazole, 4-methyl-2-phenylimidazole, benzimidazole, and 2-phenylbenzimidazole; pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, 2-methyl-4-phenylpyridine, nicotine, nicotinic acid, nicotinamide, quinoline, Pyridines such as 4-hydroxyquinoline, 8-oxyquinoline and acridine; piperazines such as 1- (2-hydroxyethyl) piperazine, pyrazine, pyrazole, pyridazine, quinosaline, purine, pyrrolidine, piperidine, 3-piperidine Roh-1,2-propanediol, morpholine, 4-methylmorpholine, 1,4-dimethylpiperazine, 1,4-diazabicyclo [2.2.2] octane.

  These acid diffusion control agents (C) may be used alone or in admixture of two or more. The compounding amount of the acid diffusion controller is usually 150 mol% or less, preferably 100 mol% or less, more preferably 70 mol% or less with respect to the acid generator. In this case, when the compounding amount of the acid diffusion control agent exceeds 150 mol%, the sensitivity and developability of the exposed area tend to decrease as a resist.

  Examples of the dissolution control agent include compounds having an effect of controlling the dissolution contrast and / or dissolution rate when used as a resist. The blending amount of the dissolution control agent is usually 50 parts by mass or less, preferably 30 parts by mass or less with respect to 100 parts by mass of the total polysiloxane. In this case, if the blending amount of the dissolution control agent exceeds 50 parts by mass, the heat resistance tends to decrease as a resist, which is not preferable.

  The surfactant is a component having an effect of improving coatability, striation, developability, and the like. For example, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene n- In addition to nonionic surfactants such as octylphenyl ether, polyoxyethylene n-nonylphenyl ether, polyethylene glycol dilaurate, and polyethylene glycol distearate, the following trade names are KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No. . 75, no. 95 (above, manufactured by Kyoeisha Chemical Co., Ltd.), F-top EF301, EF303, EF352 (above, manufactured by Tochem Products Co., Ltd.), Megafax F171, F173 (above, Dainippon Ink & Chemicals, Inc.) Manufactured), FLORARD FC430, FC431 (above, manufactured by Sumitomo 3M), Asahi Guard AG710, Surflon S-382, SC-101, SC-102, SC-103, SC-104, SC -105, SC-106 (above, manufactured by Asahi Glass Co., Ltd.) and the like. These surfactants may be used alone or in admixture of two or more. The compounding amount of the surfactant is usually 2 parts by mass or less with respect to 100 parts by mass of the total polysiloxane. Examples of additives other than those mentioned above include antihalation agents, adhesion assistants, storage stabilizers, and antifoaming agents.

Storage stabilizer:
As the storage stabilizer, an acid dissociation constant (pKa value) of 4 or less and a compound that is soluble in the solvent used in the radiation-sensitive resin composition of the present invention are preferable. The compound is not particularly limited as long as it does not adversely affect the radiation-sensitive resin composition of the present invention. For example, on the Internet, the compound of Peterson Lab. Of Chemistry Department of the Pennsylvania State University. In the list of pKa values disclosed in the site (URL address: http://research.chem.psu.edu/brpgroup/pKa_compilation.pdf), compounds with a pKa value of 4 or less are listed. Specifically, phosphoric acid which may have a substituent, and its derivative; phosphonic acid which may have a substituent, and its derivative; carboxylic acid which may have a substituent, and its Derivatives: sulfonic acids that may have a substituent, and derivatives thereof. These compounds may be used alone or in admixture of two or more. The amount used is preferably 5 parts by mass or less based on 100 parts by mass of the total polysiloxane. Examples of additives other than those mentioned above include antihalation agents, adhesion assistants, and antifoaming agents.

Preparation of composition solution:
When the radiation sensitive resin composition of the present invention is used, it is dissolved in a solvent so that the total solid content is usually 1 to 25% by mass, preferably 2 to 15% by mass. It is prepared as a composition solution by filtering with a filter of about 2 μm.

  The solvent used for the preparation of the composition solution is not particularly limited as long as it does not adversely affect the radiation-sensitive resin composition of the present invention. For example, 2-butanone, 2-pentanone, 3-methyl-2- Linear or branched ketones such as butanone, 2-hexanone, 4-methyl-2-pentanone, 3-methyl-2-pentanone, 3,3-dimethyl-2-butanone, 2-heptanone, 2-octanone Cyclic cyclic ketones such as cyclopentanone, 3-methylcyclopentanone, cyclohexanone, 2-methylcyclohexanone, 2,6-dimethylcyclohexanone, isophorone; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono- n-propyl ether acetate, propi Propylene glycol mono-i-propyl ether acetate, propylene glycol mono-n-butyl ether acetate, propylene glycol mono-i-butyl ether acetate, propylene glycol mono-sec-butyl ether acetate, propylene glycol mono-t-butyl ether acetate, etc. Alkyl ether acetates;

  Methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, n-propyl 2-hydroxypropionate, i-propyl 2-hydroxypropionate, n-butyl 2-hydroxypropionate, i-butyl 2-hydroxypropionate, Alkyl 2-hydroxypropionates such as sec-butyl 2-hydroxypropionate and t-butyl 2-hydroxypropionate; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy Alkyl 3-alkoxypropionates such as ethyl propionate;

  2,3-difluorobenzyl alcohol, 2,2,2-trifluoroethanol, 1,3-difluoro-2-propanol, 1,1,1-trifluoro-2-propanol, 3,3,3-trifluoro- 1-propanol, 2,2,3,3,4,4,4-heptafluoro-1-butanol, 2,2,3,3,4,4,5,5-octafluoro-1-pentanol, 3 , 3,4,4,5,5,5-heptafluoro-2-pentanol, 1H, 1H-perfluoro-1-octanol, 1H, 1H, 2H, 2H-perfluoro-1-octanol, 1H, 1H , 9H-perfluoro-1-nonanol, 1H, 1H, 2H, 3H, 3H-perfluorononane-1,2-diol, 1H, 1H, 2H, 2H-perfluoro-1-decanol, 1H, 1 , 2H, 3H, fluorine-containing alcohols such as 3H- perfluoro undecanoic 1,2-diol;

  2,2,2-trifluoroethyl butyrate, ethyl heptafluorobutyrate, ethyl heptafluorobutyl acetate, ethyl hexafluoroglutarate, ethyl-3-hydroxy-4,4,4-trifluorobutyrate, ethyl-2 -Methyl-4,4,4-trifluoroacetoacetate, ethyl pentafluorobenzoate, ethyl pentafluoropropionate, ethyl pentafluoropropionate, ethyl perfluorooctanoate, ethyl-4,4,4-trifluoroacetate Acetate, ethyl-4,4,4-trifluorobutyrate, ethyl-4,4,4-trifluorocrotonate, ethyl trifluorosulfonate, ethyl-3- (trifluoromethyl) butyrate, ethyl trifluoropyruvate, Ethyl trifluoroa Tate, isopropyl-4,4,4-trifluoroacetoacetate, methyl perfluorodecanoate, methyl perfluoro (2-methyl-3-oxahexanoate), methyl perfluorononanoate, methyl perfluorooctanoate Methyl-2,3,3,3-tetrafluoropropionate, methyltrifluoroacetoacetate, methyltrifluoroacetoacetate, perfluoro (2,5,8-trimethyl-3,6,9-trioxadodecanoic acid ) Methyl, propylene glycol trifluoromethyl ether acetate, propylene glycol methyl ether trifluoromethyl acetate, n-butyl trifluoromethyl acetate, methyl 3-trifluoromethoxypropionate, 1,1,1-trifluoro-2-propiate Acetate, fluorine-containing esters, such as trifluoroacetic acid n- butyl;

  2-fluoroanisole, 3-fluoroanisole, 4-fluoroanisole, 2,3-difluoroanisole, 2,4-difluoroanisole, 2,5-difluoroanisole, 5,8-difluoro-1,4-benzodioxane, tri Fluoroacetaldehyde ethyl hemiacetal, 2H-perfluoro (5-methyl-3,6-dioxanonane), 2H-perfluoro (5,8,11,14-tetramethyl-3,6,9,12,15-pentaoxa Fluorine-containing ethers such as octadecane), (perfluoro-n-butyl) tetrahydrofuran, perfluoro (n-butyltetrahydrofuran), propylene glycol trifluoromethyl ether;

  2,4-difluoropropiophenone, fluorocyclohexane, 1,1,1,2,2,3,3-heptafluoro-7,7-dimethyl-4,6-octanedione, 1,1,1,3 5,5,5-heptafluoropentane-2,4-dione, 3,3,4,4,5,5,5-heptafluoro-2-pentanone, 1,1,1,2,2,6,6 , 6-octafluoro-2,4-hexanedione, trifluorobutanol-1,1,1-trifluoro-5-methyl-2,4-hexanedione, fluorine-containing ketones such as perfluorocyclohexanone; trifluoroacetamide , Fluorine-containing amines such as perfluorotributylamine, perfluorotrihexylamine, perfluorotripentylamine, perfluorotripropylamine; Ruorotoruen, perfluorodecalin, perfluoro (1,2-dimethylcyclohexane), other fluorine-containing solvent of the fluorine-substituted cyclic hydrocarbons such as perfluoro (1,3-dimethylcyclohexane),

  n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, t-butyl alcohol, cyclohexanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether , Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol di-n-propyl ether, diethylene glycol di-n-butyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, propylene glycol monomethyl ether , Propylene glycol monoethyl Ether, propylene glycol mono -n- propyl ether,

  Toluene, xylene, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3 -Methyl-3-methoxybutyl propionate, 3-methyl-3-methoxybutyl butyrate, ethyl acetate, n-propyl acetate, n-butyl acetate, methyl acetoacetate, ethyl acetoacetate, methyl pyruvate, ethyl pyruvate N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, benzyl ethyl ether, di-n-hexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, caproic acid, caprylic acid, 1-o Pentanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, .gamma.-butyrolactone, ethylene carbonate and propylene carbonate.

  These solvents may be used alone or in admixture of two or more. Among these, linear, branched ketones or cyclic ketones, propylene glycol monoalkyl ether acetate, alkyl 2-hydroxypropionate, alkyl 3-alkoxypropionate, fluorine-containing solvents and the like are preferable.

Resist pattern formation method:
In the radiation-sensitive resin composition of the present invention, an acid is generated from the acid generator upon exposure, and the acid-dissociable group in the polysiloxane (A) is dissociated by the action of the acid, so that an acid function such as a carboxyl group is generated. As a result, the solubility of the exposed portion of the resist in the alkaline developer is increased, and the exposed portion is dissolved and removed by the alkaline developer to obtain a positive resist pattern.

When forming a resist pattern from the radiation-sensitive resin composition of the present invention, the composition solution is coated with, for example, a silicon wafer or aluminum by an appropriate application means such as spin coating, cast coating or roll coating. A resist film is formed by coating on a wafer or a substrate on which a lower layer film has been formed in advance, and in some cases, a heat treatment (hereinafter may be abbreviated as “PB”) is performed. After that, the resist film is exposed to form a predetermined resist pattern. As the radiation used at that time, F ₂ excimer laser (wavelength 157 nm) or far ultraviolet rays represented by ArF excimer laser (wavelength 193 nm), electron beam, X-ray, etc. are preferable.

In the present invention, it is preferable to perform a heat treatment (hereinafter sometimes abbreviated as “PEB”) after exposure. By this PEB, the dissociation reaction of the acid dissociable group proceeds smoothly. The heating condition of PEB varies depending on the composition of the radiation sensitive resin composition, but is usually 30 to 200 ° C, preferably 50 to 170 ° C.
In the present invention, in order to maximize the potential of the radiation-sensitive resin composition, an organic or inorganic underlayer film can be formed on the substrate to be used (for example, Japanese Patent Publication No. 6). In addition, a protective film can be provided on the resist film to prevent the influence of basic impurities and the like contained in the environmental atmosphere (see, for example, Japanese Patent Laid-Open No. 5-188598). Alternatively, these techniques can be used in combination.

Next, the exposed resist film is developed to form a predetermined resist pattern. Examples of the developer used for development include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, Triethylamine, methyldiethylamine, ethyldimethylamine, triethanolamine, tetramethylammonium hydroxide, pyrrole, piperidine, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1,5-diazabicyclo- [ 4.3.0] An alkaline aqueous solution in which at least one alkaline compound such as 5-nonene is dissolved is preferable.
The concentration of the alkaline aqueous solution is usually 10% by mass or less. In this case, if the concentration of the alkaline aqueous solution exceeds 10% by mass, the unexposed area may be dissolved in the developer, which is not preferable.

  Further, an organic solvent can be added to the developer composed of the alkaline aqueous solution, for example, acetone, 2-butanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, 3-methylcyclopentanone. , Ketones such as 2,6-dimethylcyclohexanone; methyl alcohol, ethyl alcohol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, t-butyl alcohol, cyclopentanol, cyclohexanol, 1,4-hexanediol Alcohols such as 1,4-hexane dimethylol; ethers such as tetrahydrofuran and dioxane; esters such as ethyl acetate, n-butyl acetate and i-amyl acetate; aromatic hydrocarbons such as toluene and xylene; phenol and acetonyl acetone , Dimethyl Formamide, and the like. These organic solvents may be used alone or in admixture of two or more. The amount of the organic solvent used is preferably 100% by volume or less with respect to the alkaline aqueous solution. When the amount of the organic solvent used exceeds 100% by volume, the developability is lowered, and there is a possibility that the remaining development in the exposed area may increase. Further, an appropriate amount of a surfactant or the like may be added to the developer composed of an alkaline aqueous solution. In addition, after developing with the developing solution which consists of alkaline aqueous solution, generally it wash | cleans with water and dries.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples. Here, the “part” described below is based on mass.

  Moreover, the silane compound (I) used in the present Example was produced based on the production methods described in JP-A-2002-105086 and JP-A-2002-128788. Triethoxysilane is commercially available, and the commercially available product was used as it was.

Weight average molecular weight measurement:
Mw of the polysiloxane obtained in the following Examples 1 to 5 and Comparative Example 1 uses a GPC column (2 G2000HXL, 1 G3000HXL, 1 G4000HXL) manufactured by Tosoh Corporation, and a flow rate of 1.0 ml / min. Measurement was performed by gel permeation chromatography (GPC) using monodisperse polystyrene as a standard under the analysis conditions of elution solvent: tetrahydrofuran and column temperature: 40 ° C.

Solid concentration measurement:
The solid content concentration of the polysiloxane obtained in the following Examples 1 to 5 and Comparative Example 1 is such that the polysiloxane solution placed in an aluminum cup is heated on a hot plate heated to 170 ° C. to change the mass. The solid content concentration was calculated as mass%.

Metal content measurement:
The platinum content in the siloxane compound (I), which is a raw material compound in the following Synthesis Examples 1 to 5, and the polysiloxanes obtained in the following Examples 6 to 12 and Comparative Example 1, was measured by ICP-MS. The silane compounds (I) in Synthesis Examples 1 to 6 below are all purified in advance by distillation, and all of them have a metal content equal to or lower than the measurement limit (less than 5 ppb).

Example 1 (Production of polysiloxane (1))
In a three-necked flask equipped with a stirrer, a reflux condenser, and a thermometer, a silane compound represented by the following formula (a-1) (hereinafter abbreviated as “compound (a-1)”). 3.93 g, 6.07 g of triethoxysilane, 10 g of 4-methyl-2-pentanone, and 3.39 g of an aqueous 1.72% by mass oxalic acid solution were charged and reacted at 80 ° C. for 6 hours with stirring. Thereafter, the reaction vessel was ice-cooled to stop the reaction, and the resulting reaction solution was transferred to a separating funnel, and ion-exchanged water was added and washed with water until the reaction solution became neutral. The organic layer obtained by liquid separation was substituted with 2-heptanone to obtain 22.2 g of a polysiloxane (1) solution (solid content concentration 20.5%, yield 93.4%). Mw of the polysiloxane (1) was 13,500.

Example 2 (Production of polysiloxane (2))
In a three-necked flask equipped with a stirrer, a reflux condenser, and a thermometer, 5.26 g of compound (a-1), 4.74 g of triethoxysilane, 10 g of 4-methyl-2-pentanone, and 1.72 masses. % Aqueous oxalic acid solution (3.03 g) was added, and the mixture was reacted at 80 ° C. for 6 hours with stirring. Thereafter, the reaction vessel was ice-cooled to stop the reaction, the resulting reaction solution was transferred to a separatory funnel, and ion-exchanged water was added and washed with water until the reaction solution became neutral. The organic layer obtained by liquid separation was substituted with 2-heptanone to obtain 27.0 g of a polysiloxane (2) solution (solid content concentration: 19.4%, yield: 96.5%). Mw of the polysiloxane (2) was 8,500.

Example 3 (Production of polysiloxane (3))
In a three-necked flask equipped with a stirrer, a reflux condenser, and a thermometer, 7.21 g of compound (a-1), 2.79 g of triethoxysilane, 10 g of 4-methyl-2-pentanone, and 1.72 masses. A 2.49 g% aqueous oxalic acid solution was charged, and the mixture was reacted at 80 ° C. for 6 hours with stirring. Thereafter, the reaction vessel was ice-cooled to stop the reaction, and the resulting reaction solution was transferred to a separatory funnel, and ion-exchanged water was added and washed with water until the reaction solution became neutral. The organic layer obtained by liquid separation was substituted with 2-heptanone to obtain 28.5 g of a polysiloxane (3) solution (solid content concentration 21.0%, yield 96.1%). Mw of polysiloxane (3) was 2,500.

Example 4 (Production of polysiloxane (4))
In a three-necked flask equipped with a stirrer, a reflux condenser, and a thermometer, a silane compound represented by the following formula (a-2) (hereinafter abbreviated as “compound (a-2)”). 4.83 g, 5.17 g of triethoxysilane, 10 g of 4-methyl-2-pentanone, and 3.18 g of an aqueous 1.72% by mass oxalic acid solution were charged and reacted at 80 ° C. for 6 hours with stirring. Thereafter, the reaction vessel was ice-cooled to stop the reaction, and the resulting reaction solution was transferred to a separating funnel, and ion-exchanged water was added and washed with water until the reaction solution became neutral. The organic layer obtained by liquid separation was subjected to solvent substitution with 2-heptanone to obtain 21.2 g of a polysiloxane (4) solution (solid content concentration 22.0%, yield 93.0%). Mw of the polysiloxane (4) was 7,900.

Example 5 (Production of polysiloxane (5))
In a three-necked flask equipped with a stirrer, a reflux condenser, and a thermometer, a silane compound represented by the following formula (a-3) (hereinafter abbreviated as “compound (a-3)”). 5.01 g, 4.99 g of triethoxysilane, 10 g of 4-methyl-2-pentanone, and 3.18 g of an aqueous 1.72% by mass oxalic acid solution were charged and reacted at 80 ° C. for 6 hours with stirring. Thereafter, the reaction vessel was ice-cooled to stop the reaction, and the resulting reaction solution was transferred to a separating funnel, and ion-exchanged water was added and washed with water until the reaction solution became neutral. The organic layer obtained by liquid separation was substituted with 2-heptanone to obtain 22.4 g of a polysiloxane (5) solution (solid content concentration: 21.3%, yield: 92.1%). Mw of polysiloxane (5) was 7,600.

Example 6 (Production of polysiloxane (6))
In a three-necked flask equipped with a stirrer, a reflux condenser, and a thermometer, 4.88 g of compound (a-1), 2.20 g of triethoxysilane, 2.91 g of triethoxy-2-cyanoethylsilane, and 4-methyl 2-Pentanone 10 g and 1.72% by mass oxalic acid aqueous solution 2.81 g were charged and reacted at 80 ° C. for 6 hours with stirring. Thereafter, the reaction vessel was ice-cooled to stop the reaction, and the resulting reaction solution was transferred to a separating funnel, and ion-exchanged water was added and washed with water until the reaction solution became neutral. The organic layer obtained by liquid separation was substituted with 2-heptanone to obtain 26.0 g of a polysiloxane (6) solution (solid content concentration 20.5%, yield 92.9%). Mw of polysiloxane (6) was 3,100.

Comparative Example 1 (Production of polysiloxane (R1))
In a four-necked flask equipped with a stirrer, reflux condenser, thermometer, and nitrogen bubbler, 5 g of p-toluenesulfonic acid monohydrate and 495 g of toluene were mixed and vigorously stirred. A solution prepared by dissolving 50.8 g of trichlorosilane in 250 g of toluene was added dropwise thereto and reacted at room temperature for 6 hours. The obtained reaction solution was transferred to a separatory funnel, ion-exchanged water was added, and washing with water was repeated 5 times. Then, the solvent of the organic layer was distilled off under reduced pressure to prepare a 20% by mass solution to prepare a polymerization solution (A).

  Meanwhile, in a four-necked flask equipped with a stirrer, reflux condenser, thermometer, and nitrogen bubbler, 19.43 g of norbornene-t-butyl ester and 19.43 g of toluene were added and stirred, and the catalyst concentration was 200 ppm. As such, 1,3-diethenyl-1,1,3,3-tetramethyldisiloxane complex (platinum, concentrated) was added. 87.62 g of the above polymerization solution (A) was slowly added thereto, and then the reaction was carried out for 8 hours under stirring and reflux conditions. Thereafter, the reaction vessel was ice-cooled to stop the reaction, and the resulting reaction solution was transferred to a separating funnel, and ion-exchanged water was added and washed with water until the reaction solution became neutral. The organic layer obtained by liquid separation was substituted with 2-heptanone to obtain 167.6 g of a polysiloxane (R1) solution (solid content concentration 20.5%, yield 93.0%). The Mw of the polysiloxane (R1) was 6,500.

Preparation example (preparation of composition for forming underlayer film)
A separable flask equipped with a thermometer was charged with 100 parts of acenaphthylene, 78 parts of toluene, 52 parts of dioxane and 3 parts of azobisisobutyronitrile in a nitrogen atmosphere and stirred at 70 ° C. for 5 hours. Thereafter, 5.2 parts of p-toluenesulfonic acid monohydrate and 40 parts of paraformaldehyde were added, the temperature was raised to 120 ° C., and the mixture was further stirred for 6 hours. The obtained reaction solution was put into a large amount of i-propyl alcohol, and the precipitated polymer was filtered off and dried under reduced pressure at 40 ° C. to obtain a polymer having Mw of 22,000.

  Then 10 parts of the polymer obtained, 0.5 parts of bis (4-t-butylphenyl) iodonium 10-camphor-sulfonate, and 4,4 ′-[1- {4- (1- [4-hydroxyphenyl]] -1-methylethyl) phenyl} ethylidene] bisphenol 0.5 part, cyclohexanone 89 parts were dissolved, and the resulting solution was filtered through a membrane filter having a pore size of 0.03 μm to prepare a composition for forming an underlayer film. .

Examples 7 to 12 and Comparative Example 2 (Production of radiation-sensitive resin composition)
For the polysiloxane solutions (1) to (5) and (R-1) obtained in Examples 1 to 6 and Comparative Example 1, respectively, acid generator (B), 1300 parts of 2-heptanone, and necessary In accordance with the acid diffusion control agent (C), a uniform solution was prepared to prepare each radiation sensitive resin composition (respectively referred to as Examples 7 to 12 and Comparative Example 2). The platinum content of each obtained radiation sensitive resin composition was measured, and the results are shown in Table 1.

Development defect inspection:
Each of the radiation-sensitive resin compositions obtained in Examples 7 to 12 and Comparative Example 2 was applied by spin coating onto a substrate on which a lower layer film (β-1) was previously formed on the surface of a silicon wafer. Then, PB was performed on a hot plate at 85 ° C. for 90 seconds to form a resist film having a thickness of 1,500 mm. Here, the lower layer film (β-1) is formed by applying the lower layer film forming composition on a silicon wafer by spin coating, and then on a hot plate at 180 ° C. for 60 seconds, and further at 300 ° C. for 120 seconds. It is a film having a thickness of 3,000 mm formed by baking. Next, each resist film was exposed with an ArF excimer laser (wavelength 193 nm, NA = 0.78, σ = 0.85, 2/3 annular illumination) while changing the exposure amount, and 95 on a hot plate. PEB was performed at 90 ° C. for 90 seconds. Thereafter, the resist film was developed with a 2.38 mass% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 60 seconds, washed with water, and dried to form a positive resist pattern.

  At this time, an exposure amount for forming a line and space pattern (1L1S) having a line width of 90 nm was defined as an optimum exposure amount (Eop), and this optimum exposure amount was defined as sensitivity.

  With respect to the substrate for developing defect inspection, the developing defect was evaluated using a defect inspection apparatus KLA2351 (trade name) manufactured by KLA-Tencor Corporation. The number of development defects is calculated by setting the pixel size of the defect inspection apparatus to 0.16 μm, setting the threshold value to 13, measuring in the array mode, and developing defects extracted from the difference caused by the comparison image and pixel unit overlap. Was detected and evaluated. The results are shown in Table 1.

  From this table, it can be seen that in the radiation-sensitive resin composition of the present invention, the number of development defects is significantly reduced as compared with a composition containing a large amount of platinum (Comparative Example 2).

Storage stability test:
The polysiloxane solution (2) obtained in Example 2 was mixed with the storage stabilizer (D), 1300 parts of 2-heptanone, and 5 parts of water to prepare each composition (Examples 12 to 16 and To do). Separately, the polysiloxane solution (2) obtained in Example 2 was mixed with 1300 parts of 2-heptanone and 5 parts of water to prepare a composition (this is referred to as Comparative Example 3). Next, each composition was immersed in a 60 ° C. warm bath and allowed to stand for 12 hours under stirring, and the molecular weight of each composition before and after heating was measured. The results are shown in Table 2.

Evaluation of influence of solvent in radiation-sensitive resin composition:
The polysiloxane solution (2) obtained in Example 2 was mixed with the acid generator (B) and 1300 parts of the solvent (E) to obtain a uniform solution, and each radiation-sensitive resin composition was prepared (respectively Examples 17 to 20). Next, in the same manner as the above development defect inspection, a resist pattern is formed, and an exposure amount for forming a line and space pattern (1L1S) having a line line width of 90 nm is set as an optimal exposure amount (Eop). The exposure amount was defined as sensitivity. Next, the sensitivity at the time of sample preparation and after storage for 1 month at room temperature was measured, and the storage stability was evaluated using the rate of change in sensitivity before and after storage. The results are shown in Table 3.

  According to the present invention, as a chemically amplified resist, a radiation-sensitive resin composition capable of significantly reducing development defects while maintaining good characteristics based on polysiloxane (A) and sufficient basic performance as a resist, and It is possible to provide a polysiloxane useful as a component of the radiation-sensitive resin composition. Therefore, the radiation-sensitive resin composition can be used particularly suitably for the production of LSIs that are expected to be increasingly miniaturized in the future.

Claims (5)

The following general formula (I)

(In the formula, each R ¹ independently represents an alkoxyl group having 1 to 20 carbon atoms, an acyloxy group having 2 to 7 carbon atoms, or a halogen atom, and R ² may have a substituent. A good divalent hydrocarbon group having 1 to 20 carbon atoms, and R ³ represents a monovalent acid-dissociable group.), The following general formula (II)

(In formula, each R < ⁴ > shows a C1-C20 alkoxyl group, a C2-C7 acyloxy group, or a halogen atom each independently.)
The following general formula (III), obtained by polycondensation of a silane compound represented by

(Wherein R ² and R ³ are as defined above), and the following formula (IV):

A polysiloxane having a structural unit represented by: The following general formula (I)

(In the formula, each R ¹ independently represents an alkoxyl group having 1 to 20 carbon atoms, an acyloxy group having 2 to 7 carbon atoms, or a halogen atom, and R ² may have a substituent. A good divalent hydrocarbon group having 1 to 20 carbon atoms, and R ³ represents a monovalent acid-dissociable group), and the following general formula (II)

(In formula, each R < ⁴ > shows a C1-C20 alkoxyl group, a C2-C7 acyloxy group, or a halogen atom each independently.)
The following general formula (III), obtained by polycondensation of a silane compound represented by

(Wherein R ² and R ³ are as defined above), and the following formula (IV):

A radiation-sensitive resin composition comprising a polysiloxane having a structural unit represented by formula (I) and a radiation-sensitive acid generator. The following general formula (I)

(In the formula, each R ¹ independently represents an alkoxyl group having 1 to 20 carbon atoms, an acyloxy group having 2 to 7 carbon atoms, or a halogen atom, and R ² may have a substituent. A good divalent hydrocarbon group having 1 to 20 carbon atoms, and R ³ represents a monovalent acid-dissociable group.), The following general formula (II)

(In formula, each R < ⁴ > shows a C1-C20 alkoxyl group, a C2-C7 acyloxy group, or a halogen atom each independently.)
A silane compound represented by the following general formula (III) by polycondensation in the presence of water:

(Wherein R ² and R ³ are as defined above), and the following formula (IV):

The manufacturing method of polysiloxane which has a structural unit represented by these. The polysiloxane according to claim 1, wherein the metal content is 200 ppb or less. A radiation-sensitive resin composition comprising the polysiloxane according to claim 4 and a radiation-sensitive acid generator.