KR20070018795A - Silane compound, polysiloxane and radiation-sensitive resin composition - Google Patents

Abstract

The present invention discloses novel polysiloxanes which are particularly suitable as resin components in chemically amplified resists which are excellent in I-D bias, focal conductance (DOF) and the like. Moreover, this invention discloses the novel silane compound useful as a raw material which synthesize | combines the said polysiloxane, and the radiation sensitive resin composition containing the said polysiloxane. The silane compound is represented by the following general formula (I). Polysiloxane has a structural unit represented by following formula (1). The radiation sensitive resin composition contains the said polysiloxane and a radiation sensitive acid generator.

<Formula I>

<Formula 1>

(R represents an alkyl group, R ¹ and R ² represent a fluorine atom, a lower alkyl group or a lower fluorinated alkyl group, n is 0 or 1, k is 1 or 2, i is an integer of 0 to 10.)

Silane compound, polysiloxane, radiation sensitive acid generator, radiation sensitive resin composition, chemically amplified resist

Description

Silane compounds, polysiloxanes and radiation sensitive resin compositions {SILANE COMPOUND, POLYSILOXANE AND RADIATION-SENSITIVE RESIN COMPOSITION}

The present invention relates to a radiation sensitive resin composition containing a novel silane compound, a novel polysiloxane, and the polysiloxane, and suitable for fine processing using radiation such as far ultraviolet rays, electron beams, and X-rays.

In recent years, the demand for higher density and higher integration of LSI (highly integrated circuit) is increasing, and along with this, the miniaturization of wiring patterns is rapidly progressing.

As one of the means capable of coping with such miniaturization of the wiring pattern, there is a method of shortening the radiation used in the lithography process, and recently, ultraviolet rays such as g-ray (wavelength 436 nm) and i-ray (wavelength 365 nm) Instead, far ultraviolet rays such as KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F2 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 (vinyl phenol), etc. have been used as a resin component, but since these materials contain an aromatic ring in a structure, and there exists strong absorption in the wavelength of 193 nm, For example, in the lithography process using an ArF excimer laser, high precision corresponding to high sensitivity, high resolution, and high aspect ratio cannot be obtained.

Therefore, there is a need for a resin material for resists that is transparent to 193 nm or less, in particular, to an ArF excimer laser (wavelength 193 nm), an F2 excimer laser (wavelength 157 nm), or the like and has a dry etching resistance equal to or higher than an aromatic ring. . A siloxane polymer can be considered as one of them, and MITR. R. Kunz et al. Present measurement results that polysiloxane polymers are excellent in transparency at wavelengths of 193 nm or less, especially 157 nm, and resist materials in lithography processes in which the polymer uses wavelengths of 193 nm or less. (See, eg, J. Photopolym. Sci. Technol., Vol. 12, No. 4 (1999) P.561-570, SPIE, Vol. 3678 (1999) P. 13-23). ). In addition, polysiloxane polymers are known to have excellent dry etching resistance, and among them, resists containing polyorganopolysilsesquioxane having a ladder structure have high plasma resistance.

On the other hand, several reports have already been made on chemically amplified resistors using siloxane polymers. That is, the radiation sensitive resin composition using the polysiloxane which has an acid dissociable group in the side chain by which acid dissociable groups, such as a carboxylic ester group and a phenol ether group, couple | bonded with the silicon atom through one or more carbon atoms is disclosed (for example, , Japanese Unexamined Patent Application Publication No. 5-323611). However, in this polysiloxane, the resolution can be increased only when the acid dissociable carboxylic acid ester group of the side chain is efficiently dissociated, and when most of the acid dissociable groups are dissociated, the curing shrinkage stress of the resist film becomes large, and the crack or peeling of the resist film is increased. There is a problem that it is easy to cause a back.

In addition, a positive resist using a polymer in which a carboxyl group of poly (2-carboxyethylsiloxane) is protected by an acid dissociable group such as t-butyl group is disclosed (see, for example, Japanese Unexamined Patent Application Publication No. 8-160623). ). However, in this resist, since the protection rate of a carboxyl group is low, many carboxylic acid components exist in an unexposed part, and developing with a normal alkaline developing solution is difficult.

Moreover, the resist resin composition using the polyorgano silsesquioxane which has an acid dissociative ester group is disclosed (for example, refer Unexamined-Japanese-Patent No. 11-60733). However, this polyorgano silsesquioxane is manufactured by addition-reacting an acid dissociable group containing (meth) acrylic monomer to condensation products, such as vinyltrialkoxysilane and (gamma)-methacryloxypropyl trialkoxysilane, and is a polymer. Since unsaturated groups derived from a (meth) acrylic monomer remain in the side chain, there is a problem in terms of transparency at a wavelength of 193 nm or less. The publication also discloses a resist resin composition using a polymer obtained by esterifying polyhydroxycarbonylethylsilsesquioxane with t-butyl alcohol, which also has a low carboxyl group-protection rate and is a Japanese patent as a resist. There is a problem similar to that of JP-A-8-160623.

In addition, in the chemically amplified resist using the siloxane-based polymer as described above, the acid dissociable groups in the siloxane-based polymer can dissociate at a relatively low temperature, so that the temperature of the heat treatment after the exposure can be lowered. It is also desired that the acid diffusion caused by the reaction can be appropriately suppressed, so that when the line and space pattern is formed, the line width of the line pattern is hard to fluctuate due to the density of the pattern (that is, the ID bias) is excellent.

In addition, Japanese Unexamined Patent Application Publication No. 2002-268225 discloses a carboxylic acid ester group and a fluorine atom esterified with an acid labile group (t-butyl group, 1-methylcyclohexyl group, 1-ethylcyclopentyl group, etc.) or A high molecular compound having a cyclic organic group substituted with a fluoroalkyl group and having a siloxane repeating unit in which the cyclic organic group is bonded to a silicon atom, more specifically 2-t-butoxycarbonyl-2-trifluoromethyl-5 ( 6) polycondensates of trichlorosilyl norbornane with 2-hydroxy-2-trifluoromethyl-5 (6) -trichlorosilyl norbornane or 2-t-butoxycarbonyl-2-tri Fluoromethyl-5 (6) -trichlorosilylnorbornane and 2- [2-hydroxy-2,2-di (trifluoromethyl) ethyl] -5 (6) -trichlorosilylnorbornane Chemically amplified resists containing polycondensates, and the polymer compounds are disclosed. The sensitivity, resolution and plasma etching resistance is to be superior.

On the other hand, in recent chemically amplified resists, process margins such as ID bias and focal conductance (DOF) are important characteristics, including the case of using a siloxane polymer as the resist pattern becomes finer. There is a strong demand for chemically amplified resists with excellent balance of properties including such process margins.

An object of the present invention is to provide a radiation sensitive resin composition having a high transparency at a wavelength of 193 nm or less and particularly useful as a chemically amplified resist having excellent property balance including process tolerances such as ID bias and focus conduction (DOF). It is providing the novel polysiloxane suitable as a resin component of the.

Another object of the present invention is to provide a radiation-sensitive resin composition containing the polysiloxane and useful as a chemically amplified resist having excellent property balance including the process tolerance.

Another object of the present invention is to provide a novel silane compound useful as a raw material for synthesizing the polysiloxane.

Other objects and advantages of the present invention will become apparent from the following description.

The present invention, first,

The silane compound (henceforth a "silane compound (I)") represented by following formula (I) is included.

In formula (I), each R independently of each other represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and R ¹ and R ² are each independently a fluorine atom, a straight or branched carbon group of 1 to 4 carbon atoms. An alkyl group or a linear or branched fluorinated alkyl group having 1 to 4 carbon atoms, n is 0 or 1, k is 1 or 2, and i is an integer of 0 to 8 when k = 1, k = 2 Is an integer of 0 to 10.]

In the formula (I), when n = 0, the silicon atom is bonded to the 2- or 3-position of the norbornane ring, and the carbon atom forming the -COO- group is bonded to the 5- or 6-position of the norbornane ring And when n = 1, the silicon atom is bonded to the 4-position or 5-position of the upper tetracyclododecane ring, and the carbon atom forming the -COO- group is bonded to the 9-position or 10-position of the tetracyclododecane ring Doing.

Secondly, the present invention

Polysiloxane (weight-average molecular weight) by the gel permeation chromatography (GPC) which has a structural unit represented by following formula (1) is 500-1,000,000 (Hereinafter, it is called "polysiloxane (1)").

In Formula 1, R ¹ and R ² independently of each other represent a fluorine atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched fluorinated alkyl group having 1 to 4 carbon atoms, and n is 0 or 1, k is 1 or 2, i is an integer of 0-8 when k = 1, and an integer of 0-10 when k = 2.]

In the formula (1), when n = 0, the silicon atom is bonded to the 2-position or 3-position of the norbornane ring, and the carbon atom constituting the -COO- group is bonded to the 5- or 6-position of the norbornane ring And when n = 1, the silicon atom is bonded to the 4-position or 5-position of the upper tetracyclododecane ring, and the carbon atom forming the -COO- group is bonded to the 9-position or 10-position of the tetracyclododecane ring Doing.

Third, the present invention

(A) Polysiloxane (1) and (B) A radiation sensitive resin composition containing the radiation sensitive acid generator is included.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

Silane  Compound (Ⅰ)

In general formula (I), as a C1-C20 linear, branched or cyclic alkyl group of R, a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, 2-methylpropyl group is mentioned, for example. , 1-methylpropyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-dodecyl group, n-tetra A decyl group, n-hexadecyl group, n-octadecyl group, an acyl group, a cyclopentyl group, a cyclohexyl group, etc. are mentioned.

Among these alkyl groups, methyl group, ethyl group and the like are preferable.

In general formula (I), as a C1-C4 linear or branched alkyl group of R <^1> and R <^2> , For example, a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, 2-methyl A propyl group, 1-methylpropyl group, t-butyl group, etc. are mentioned.

Among these alkyl groups, methyl group, ethyl group and the like are preferable.

Moreover, as a C1-C4 linear or branched fluorinated alkyl group of R <^1> and R <^2> , For example, a fluoromethyl group, a trifluoromethyl group, 2,2,2- trifluoroethyl group, pentafluoro Ethyl group, 3,3,3-trifluoro-n-propyl group, 3,3,3,2,2-pentafluoro-n-propyl group, heptafluoro-n-propyl group, 4,4,4 -Trifluoro-n-butyl group, 4,4,4,3,3-pentafluoro-n-butyl group, 4,4,4,3,3,2,2-heptafluoro-n-butyl group And nonafluoro-n-butyl groups.

Among these fluorinated alkyl groups, trifluoromethyl group, 2,2,2-trifluoroethyl group, pentafluoroethyl group and the like are preferable.

In the general formula (I), R ¹ and R ^{2 are} particularly preferably fluorine atoms, methyl groups, ethyl groups, trifluoromethyl groups, 2,2,2-trifluoroethyl groups, pentafluoroethyl groups, and the like.

Moreover, as n, all 0 and 1 are preferable, As m, all 1 and 2 are preferable, and as i, 0-2 are preferable.

As a specific example of preferable silane compound (I), the compound represented by following formula (I-1-1)-formula (I-1-4), following formula (I-2-1)-formula (I-2-4) The compound represented by) is mentioned.

The silane compound (I) is, for example, a corresponding derivative or tricyclo [4.4.0.1 of triethoxysilane and bicyclo [2.2.1] hepto-2-ene, as shown in Synthesis Example 1 to be described later. ^2,5 .1 ^7,10] can be synthesized in a corresponding derivative of the dodeca-3-ene, by addition reaction in the presence of chloroplatinic acid (H2PtCl6).

The silane compound (I) can be suitably used as a raw material for synthesizing the polysiloxane (1) and the polysiloxane (1-1), and is also useful as a raw material or intermediate for synthesizing the related other silane compounds or other polysiloxanes. .

Polysiloxane  (One)

Polysiloxane (1) is polysiloxane which has a structural unit (henceforth "the structural unit (1)") represented by the said General formula (1).

The carboxylic acid ester structure in General formula (1) has comprised the acid dissociable group which dissociates by action of an acid and produces | generates a carboxyl group.

In general formula (1), as a C1-C4 linear or branched alkyl group of R <^1> and R <^2> and a C1-C4 linear or branched fluorinated alkyl group, For example, R <^1> and The same thing as the group illustrated about the C1-C4 linear or branched alkyl group of R <^2> and a C1-C4 linear or branched fluorinated alkyl group, respectively is mentioned.

In the structural unit (1), R ^{1 is} particularly preferably a methyl group, an ethyl group, a propyl group, a butyl group, or the like, and as R ² , a fluorine atom, a methyl group, an ethyl group, a trifluoromethyl group, 2,2,2 is particularly preferred. -Trifluoroethyl group, pentafluoroethyl group, etc. are preferable, as k, 1 and 2 are preferable, and as i, 0 is especially preferable.

The structural unit (1) is a unit in which the silane compound (I) is condensed at a position of three -OR groups bonded to the silicon atom, and as a preferable specific example thereof, the structural unit (I) is exemplified as the preferred specific example of (I) of the silane compound. The unit which the compound represented by said formula (I-1-1)-formula (I-1-4) or the compound represented by said formula (I-1-2)-formula (I-2-4) condensed, etc. Can be mentioned.

In the polysiloxane (1), the unit structure (1) may be present singly or in combination of two or more.

Polysiloxane (1) can have one or more structural units (henceforth "other structural unit ((alpha))") other than structural unit (1).

As another structural unit ((alpha)), a condensation reaction other than the structural unit derived from the trifunctional or tetrafunctional silane compound with respect to condensation reaction, such as a structural unit represented by following formula (3), (4) or (5), for example The structural unit derived from the bifunctional silane compound etc. are mentioned.

[Equation 3, E represents a monovalent organic group having a fluorinated hydrocarbon group.]

In formula (4), R <^4> is a C1-C20 linear or branched, cyclic, polycyclic alkyl group, C1-C20 linear or branched halogenated alkyl group, C6-C20 monovalent aromatic hydrocarbon group Or a monovalent halogenated aromatic hydrocarbon group having 6 to 20 carbon atoms.]

In the formula (3), examples of the monovalent organic group having a fluorinated hydrocarbon group of E include the group represented by the following formula (6) or formula (7).

In the formulas (6) and (7), each Y independently represents a C4-20 divalent hydrocarbon group having a cyclic skeleton, the divalent hydrocarbon group may be substituted, and each Z independently represents a hydrogen atom or a carbon number 1. The monovalent hydrocarbon group of -10 or the monovalent halogenated hydrocarbon group of 1 to 10 carbon atoms is represented. In the formula (6), either Y or Z is a group having a fluorine atom.]

In the formulas (6) and (7), examples of the divalent hydrocarbon group having 4 to 20 carbon atoms having a cyclic skeleton of Y and its substituted derivatives include 1,3-cyclobutylene group, 1,3-cyclopentylene group, 1, 3-cyclohexylene group, 1,4-cyclohexylene group, 1-trifluoromethyl-1,3-cyclohexylene group, 1-trifluoromethyl-1,4-cyclohexylene group, the following formula A group having a cycloalkane skeleton such as the group represented by (Y-1);

1,4-phenylene group, perfluoro-1,4-phenylene group, 1,4-naphthylene group, 2,3-naphthylene group, perfluoro-1,4-naphthylene group, perfluoro- A group having an aromatic skeleton such as a 2,3-naphthylene group and a group represented by the following formulas (Y-2) to (Y-3);

Groups having a Confucian-type alicyclic skeleton, such as group represented by following formula (Y-4)-(Y-19);

Etc. can be mentioned.

It is preferable that these cycloalkane skeletons, aromatic skeletons, and cyclic cyclic alicyclic skeletons are bonded directly to the silicon atoms of the formula (2) in the group having a cycloalkane skeleton, a group having an aromatic skeleton, and a group having a pedophilic alicyclic skeleton. Do.

In the formulas (6) and (7), a group having a norbornane skeleton or a tetracyclododecane skeleton is preferable, more preferably a group substituted with a fluorine atom or a trifluoromethyl group, and particularly preferably, a formula (Y -4), a group represented by formula (Y-6), formula (Y-9) or formula (Y-10) and the like.

Moreover, as a C1-C10 monovalent hydrocarbon group of Z, a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group, n-pentyl group, 3-methylbutyl group, neopentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group Linear, branched or cyclic alkyl groups such as cyclobutyl group, cyclopentyl group and cyclohexyl group; Aromatic hydrocarbons such as phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, benzyl group, phenethyl group, α-naphthyl group and β-naphthyl group; Confucian-type hydrocarbon groups, such as a norbornyl group, a tricyclo decanyl group, a tetracyclo decanyl group, an adamantyl group, etc. are mentioned.

Among these monovalent hydrocarbon groups, methyl group, ethyl group, n-propyl group, n-butyl group and the like are preferable.

Moreover, as a C1-C10 monovalent halogenated hydrocarbon group of Z, the said C1-C10 monovalent hydrocarbon group, for example, 1 or more types, such as a fluorine atom, a chlorine atom, a bromine atom, or 1 Groups substituted with one or more, preferably one or more fluorine atoms (hereinafter referred to as "monovalent fluorinated hydrocarbon groups"), and specific examples thereof include a trifluoromethyl group, a 2,2,2-trifluoro Ethyl group, pentafluoroethyl group, 3,3,3-trifluoro-n-propyl group, 3,3,3,2,2-pentafluoro-n-propyl group, heptafluoro-n-propyl group, 4,4,4-trifluoro-n-butyl group, 4,4,4,3,3-pentafluoro-n-butyl group, 4,4,4,3,3,2,2-heptafluoro Rho-n-butyl group, nonafluoro-n-butyl group, 5,5,5-trifluoro-n-pentyl group, 5,5,5,4,4-pentafluoro-n-pentyl group, 5,5,5,4,4,3,3-heptafluoro-n-heptyl group, 5,5,5,4,4,3,3,2,2-nonafluoro-n-pentyl group, Perfluoro-n-pentyl group, perflu In the like -n- octyl group.

Among these monovalent fluorinated hydrocarbon groups, trifluoromethyl group, 2,2,2-trifluoroethyl group, pentafluoroethyl group, 3,3,3-trifluoro-n-propyl group, 3,3,3, 2,2-pentafluoro-n-propyl group, heptafluoro-n-propyl group, nonafluoro-n-butyl group, perfluoro-n-pentyl group, etc. are preferable.

In the formulas (6) and (7), Z is particularly preferably a hydrogen atom, a heptafluoro-n-propyl group, or the like.

In general formula (4), as a C1-C20 linear or branched alkyl group of R <^4> , For example, a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, etc. are mentioned, C1-C20 As a linear or branched halogenated alkyl group of, trifluoromethyl group, pentafluoroethyl group, heptafluoro-n-propyl group, heptafluoro-i-propyl group, etc. are mentioned, for example, As a -20 monovalent aromatic hydrocarbon group, a phenyl group, (alpha)-naphthyl group, (beta) -naphthyl group, benzyl group, a phenethyl group etc. are mentioned, for example, As a C6-C20 monovalent halogenated aromatic hydrocarbon group, For example, pentafluorophenyl group, perfluorobenzyl group, perfluorophenethyl group, 2- (pentafluorophenyl) hexafluoro-n-propyl group, 3- ( To the other-fluorophenyl), and the like -n- propyl hexafluoropropane.

In the structural unit (4), R ^{4 is preferably a} methyl group, an ethyl group, a trifluoromethyl group, a pentafluoroethyl group, a perfluorophenethyl group, a 3- (pentafluorophenyl) hexafluoro-n-propyl group, or the like. Do.

In polysiloxane (1), the content rate of the structural unit (1) is 10-100 mol% normally, Preferably it is 15-90 mol%, More preferably, it is 20-70 mol%. In this case, when the content rate of the structural unit (1) is less than 10 mol%, there is a tendency that the resolution contrast is insufficient and the resolution decreases.

Moreover, the content rate of another structural unit ((alpha)) is 5 mol% or more normally, Preferably it is 10-80 mol%, More preferably, it is 20-80 mol%. In this case, when the content rate of another structural unit ((alpha)) is less than 5 mol%, there exists a tendency for I-D bias to fall.

The polystyrene reduced weight average molecular weight (hereinafter referred to as "Mw") by gel permeation chromatography (GPC) of the polysiloxane (1) is 500 to 1,000,000, preferably 500 to 100,000, particularly preferably 500 to 40,000 to be. In this case, when Mw is less than 500, there exists a tendency for the glass transition temperature (Tg) of the polymer obtained to fall, and when it exceeds 1,000,000, the solubility to the solvent of the polymer obtained will tend to fall.

The polysiloxane (1) has high transparency to radiation having a wavelength of 193 nm or less, excellent dry etching resistance, and particularly excellent ID bias, and particularly, fine particles using radiation such as far ultraviolet rays, electron beams, and X-rays. In addition to being suitably used as a resin component in chemically amplified resists for processing, they are useful alone or as a mixture with various other polysiloxanes, for example, in molded articles, films, laminate materials, paints and the like.

Polysiloxane  (1-1)

Moreover, as polysiloxane (1), it has the structural unit (1) and the structural unit represented by following formula (2) except a structural unit (1) (henceforth "a structural unit (2)"). Polysiloxane (henceforth "polysiloxane (1-1)") is also preferable.

In Formula 2, each R ³ independently represents 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 derivative thereof, or any two R ^{3 's} These mutual bonds form a divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof together with the carbon atoms to which each is bonded, and the remaining R ³ is a linear or branched alkyl group having 1 to 4 carbon atoms or carbon atoms. 4-20 monovalent alicyclic hydrocarbon group or its derivative, and m is 0 or 1.]

In formula (2), when m = 0, the silicon atom is bonded to the 2-position or 3-position of the norbornane ring, and the carbon atom constituting the -COO- group is bonded to the 5- or 6-position of the norbornane ring and And when m = 1, the silicon atom is bonded at the 4-position or 5-position of the upper tetracyclododecane ring, and the carbon atom forming the -COO- group is bonded at the 9-position or 10-position of the tetracyclododecane ring. Doing.

As a preferable specific example of structural unit (1) in polysiloxane (1-1), it is represented by said formula (I-1-1)-formula (I-1-4) illustrated as a preferable specific example of a silane compound (I). The compound which becomes the compound or the compound represented by said Formula (I-2-1)-Formula (I-2-4), etc. are mentioned, Especially the silane compound represented by said Formula (I-1-1) is mentioned. This condensed unit is preferable.

In polysiloxane (1-1), the structural unit (1) may be used alone or in combination of two or more.

In general formula (2), as a C1-C4 linear or branched alkyl group of R <^3> , For example, a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group, etc. are mentioned.

Among these alkyl groups, methyl group, ethyl group, n-propyl group and the like are preferable.

Examples of the divalent alicyclic hydrocarbon group of R ³ and C4-20 monovalent alicyclic hydrocarbon group and any two of R ³ of a cross-coupled to form together with the carbon atom to which each is bonded having 4 to 20 carbon atoms, For example, groups derived from cycloalkanes such as cyclobutane, cyclopentane, cyclohexane, cycloheptane and cyclooctane; Derived from Confucian hydrocarbons such as adamantane, bicyclo [2.2.1] heptane, tetracyclo [6.2.1.1 ^{3,6 2,7} ] dodecane, tricyclo [5.2.1.0 ^2,6 ] decane And the like.

Among these monovalent alicyclic hydrocarbon groups and divalent alicyclic hydrocarbon groups, groups derived from cyclopentane, cyclohexane, adamantane, bicyclo [2.2.1] heptane, and the like are preferable.

Moreover, as a derivative of the said monovalent or bivalent alicyclic hydrocarbon group, For example, A hydroxyl group; Carboxyl groups; Oxy group (ie, ═O group); Hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 2-hydroxybutyl group, 3-hydroxybutyl group C1-C4 hydroxyalkyl groups, such as a 4-hydroxybutyl group; C1-C4 alkoxyl groups, such as a methoxy group, an ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, 2-methylpropoxy group, 1-methylpropoxy group, and t-butoxy group ; Cyano group; The group which has 1 or more types of substituents, such as a C2-C5 cyanoalkyl group, such as a cyanomethyl group, 2-cyanoethyl group, 3-cyanopropyl group, and 4-cyanobutyl group, is mentioned.

Among these substituents, a hydroxyl group, a carboxyl group, a hydroxymethyl group, a cyano group, a cyanomethyl group and the like are preferable.

In the general formula (2), as a specific example of the structure corresponding to -C (R ³ ) ₃ ,

t-butyl group, 2-methyl-2-butyl group, 2-ethyl-2-butyl group, 3-methyl-3-butyl group, 3-ethyl-3-butyl group, 3-methyl-3-pentyl group, etc. Trialkylmethyl group;

2-methyladamantane-2-yl group, 2-methyl-3-hydroxyadamantan-2-yl group, 2-ethyladamantan-2-yl group, 2-ethyl-3-hydroxyadamantane- 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-ethoxymethyladamantan-2-yl group, 2-n-propoxymethyladamantan-2-yl 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] heptan-2-yl group, 2-methyl-5-cyanobicyclo [2.2.1] heptan-2-yl group, 2-methyl-6-cyanobicyclo [2.2.1] heptan-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] Heptane-2-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 ] dodecane -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-ethyltetra Cyclo [6.2.1.1 ^3,6 .0 ^2,7 ] dodecane-4-yl group, 4-ethyl-9-hydroxytetracyclo [6.2.1.1 ^3,6 .0 ^2,7 ] dodecane-4-yl group , 4-ethyl-10-hydroxytetracyclo [6.2.1.1 ^{3,6 2,7} ] dodecan-4-yl group,

8-methyltricyclo [5.2.1.0 ^2,6 ] decane-8-yl group, 8-methyl-4-hydroxytricyclo [5.2.1.0 ^2,6 ] decane-8-yl group, 8-methyl-4-sia Nocricyclo [5.2.1.0 ^2,6 ] decane-8-yl, 8-ethyltricyclo [5.2.1.0 ^2,6 ] decane-8-yl, 8-ethyl-4-hydroxytricyclo [5.2.1.0 ^2,6] decane-8-diary

Alkyl substituted bridged hydrocarbon groups such as these;

1-methyl-1-cyclopentylethyl group, 1-methyl-1- (2-hydroxycyclopentyl) ethyl group, 1-methyl-1- (3-hydroxycyclopentyl) ethyl group, 1-methyl-1-cyclohexyl Ethyl group, 1-methyl-1- (3-hydroxycyclohexyl) ethyl group, 1-methyl-1- (4-hydroxycyclohexyl) ethyl group, 1-methyl-1-cycloheptylethyl group, 1-methyl-1- Dialkyl cycloalkylmethyl groups such as (3-hydroxycycloheptyl) ethyl group and 1-methyl-1- (4-hydroxycycloheptyl) ethyl group;

1-methyl-1- (adamantan-1-yl) ethyl group, 1-methyl-1- (3-hydroxyadamantan-1-yl) 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 2,7} ] dodecan-4-yl) ethyl group, 1-methyl-1- ( 9-hydroxy tetracyclo [6.2.1.1 ^{3,6 2,7} ] dodecan-4-yl) ethyl group, 1-methyl-1- (10-hydroxytetracyclo [6.2.1.1 ^3,6 .0 ^2,7 ] dodecane-4-yl) ethyl group, 1-methyl-1- (tricyclo [5.2.1.0 ^2,6 ] decane-8-yl) ethyl group, 1-methyl-1- (4-hydroxytri Alkyl-substituted / crosslinked hydrocarbon group-substituted methyl groups, such as cyclo [5.2.1.0 ^2,6 ] decane-8-yl) ethyl group;

1,1-dicyclopentylethyl group, 1,1-di (2-hydroxycyclopentyl) ethyl group, 1,1-di (3-hydroxycyclopentyl) ethyl 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) Alkyl dicycloalkylmethyl groups such as an ethyl group and a 1,1-di (4-hydroxycycloheptyl) ethyl group;

1,1-di (adamantan-1-yl) ethyl group, 1,1-di (3-hydroxyadamantan-1-yl) ethyl group, 1,1-di (bicyclo [2.2.1] heptane -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] heptane -2-yl) ethyl group, 1,1-di (tetracyclo [6.2.1.1 ^{3,6 2,7} ] dodecan-4-yl) ethyl group, 1,1-di (9-hydroxytetracyclo [ 6.2.1.1 ^3,6 .0 ^2,7 ] dodecane-4-yl) ethyl group, 1,1-di (10-hydroxytetracyclo [6.2.1.1 ^{3,6 2,7} ] dodecane-4 -Yl) ethyl group, 1,1-di (tricyclo [5.2.1.0 ^2,6 ] decane-8-yl) ethyl group, 1,1-di (4-hydroxytricyclo [5.2.1.0 ^2,6 ] decane Alkyl-substituted di (crosslinked hydrocarbon group) substituted methyl groups, such as -8-yl) ethyl group

Etc. can be mentioned.

In the structural unit (2), examples of the structure corresponding to -C (R ³ ) ₃ include t-butyl group, 2-methyladamantan-2-yl group, 2-ethyladamantan-2-yl group, 2 -n-propyladamantan-2-yl group, 2-methoxymethyladamantan-2-yl group, 2-ethoxymethyladamantan-2-yl group, 2-methylbicyclo [2.2.1] heptane- 2-yl group, 2-ethylbicyclo [2.2.1] heptan-2-yl group, 1-methyl-1- (adamantan-1-yl) ethyl group, 1-methyl-1- (bicyclo [2.2.1 ] Heptan-2-yl) ethyl group etc. are preferable.

The carboxylic acid ester structure in the structural unit (2) has comprised the acid dissociable group which dissociates by action of an acid and produces | generates a carboxyl group.

In the structural unit (2), both 0 and 1 are preferable as m.

In polysiloxane (1-1), the structural unit (2) may be used alone or in combination of two or more.

Polysiloxane (1-1) can have one or more structural units (henceforth "other structural unit ((beta))") other than a structural unit (1) and a structural unit (2).

As another structural unit (β), for example, a trifunctional or tetrafunctional silane compound with respect to a condensation reaction, such as a structural unit represented by the formula (3), (4) or (5), exemplified for the other structural unit (α). In addition to the structural unit derived from, the structural unit derived from the bifunctional silane compound with respect to condensation reaction, etc. are mentioned.

In polysiloxane (1-1), content of the structural unit (1) is 3-50 mol% normally, Preferably it is 3-45 mol%, More preferably, it is 5-40 mol%. In this case, when the content of the structural unit (1) is less than 3 mol%, the resolution as a resist tends to decrease, while when it exceeds 50 mol%, the sensitivity as a resist tends to decrease.

Moreover, the content rate of the structural unit (2) is 3-50 mol% normally, Preferably it is 3-45 mol%, More preferably, it is 5-40 mol%. In this case, when the content rate of the structural unit (2) is less than 3 mol%, the resolution as a resist tends to decrease, while when it exceeds 50 mol%, the sensitivity as a resist tends to decrease.

In addition, the content rate of another structural unit ((beta)) is 85 mol% or less normally, Preferably it is 80 mol% or less. In this case, when the content rate of another structural unit exceeds 85 mol%, there exists a tendency for the resolution as a resist to fall.

The polystyrene reduced weight average molecular weight (hereinafter referred to as "Mw") by gel permeation chromatography (GPC) of polysiloxane (1-1) is 500 to 1,000,000, preferably 500 to 100,000, particularly preferably 500 40,000. In this case, when Mw is less than 500, there exists a tendency for the glass transition temperature (Tg) of resin obtained to fall, and when it exceeds 1,000,000, the solubility to the solvent of the resin obtained will tend to fall.

Polysiloxane (1-1) has high transparency to radiation having a wavelength of 193 nm or less, and is excellent in dry etching resistance, and particularly, chemically amplified resists for fine processing using radiation such as far ultraviolet rays, electron beams, and X-rays. In addition to being able to be used suitably as a resin component in the above, it is useful also in a molded article, a film, a laminate, a coating material etc., alone or in mixture with other various siloxane resins.

Polysiloxane  (1) and Polysiloxane  (1-1) Manufacturing Method

The polysiloxane (1) is polycondensed in a solvent-free or solvent, for example, under resistance conditions or under basic conditions, together with a silane compound which optionally gives a silane compound (I) to another structural unit (α). Although it can manufacture by making it carry out, it is preferable to carry out reaction manufacture under basic conditions after polycondensation under acidic conditions.

Moreover, polysiloxane (1-1) is a silane compound which gives a silane compound (I) and a structural unit (2), for example with the silane compound which gives another structural unit ((beta)) as needed, It can be prepared by polycondensation in a solvent-free or solvent under acidic conditions or under basic conditions, but is preferably prepared by polycondensation under acidic conditions and then continuing the reaction under basic conditions.

In the said polycondensation, the compound represented by following formula (8) or (9) can also be used as a silane compound which gives another structural unit ((alpha)) or another structural unit ((beta)), and each silane compound is each partially Or all may be used as partial condensates.

[In Formula 8 and Formula 9, each R 'independently of each other represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and each Y is the same as Y in Formulas 6 and 7.

Hereinafter, the polycondensation method which manufactures polysiloxane (1) and polysiloxane (1-1) is demonstrated.

In the case of polycondensation under acidic conditions, an acidic catalyst is used.

Examples of the acidic catalyst include hydrochloric acid, sulfuric acid, nitric acid, formic acid, asthic acid, n-propionic acid, butyric acid, valeric acid, oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, adipic acid, phthalic acid, terephthalic acid, and anhydride. Acetic acid, maleic anhydride, citric acid, boric acid, phosphoric acid, titanium tetrachloride, zinc chloride, aluminum chloride, benzenesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, and the like.

Among these acidic catalysts, hydrochloric acid, sulfuric acid, acetic acid, oxalic acid, malonic acid, maleic acid, fumaric acid, acetic anhydride, maleic anhydride and the like are preferable.

The said acidic catalyst can be used individually or in mixture of 2 or more types.

The use amount of the acidic catalyst is usually 0.01 to 10,000 parts by weight based on 100 parts by weight of the total amount of the silane compound.

In addition, in the case of polycondensation and reaction under basic conditions, a basic catalyst is used. Among the basic catalysts, examples of the inorganic bases include lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, potassium carbonate and the like.

Moreover, as organic bases in the said basic catalyst, it is, for example,

linear, branched or cyclic monoalkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine and cyclohexylamine;

Di-n-butylamine, di-n-pentylamine, di-n-hexylamine, di-n-heptylamine, di-n-octylamine, di-n-nonylamine, di-n-decylamine, cyclo Linear, branched or cyclic dialkylamines such as hexylmethylamine and dicyclohexylamine;

Triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, tri-n- Linear, branched or cyclic trialkylamines such as nonylamine, tri-n-decylamine, cyclohexyldimethylamine, dicyclohexylmethylamine and tricyclohexylamine;

Aromatic amines such as aniline, N-methylaniline, N, N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, 4-nitroaniline, diphenylamine, triphenylamine and naphthylamine;

Ethylenediamine, N, N, N ', N'-tetramethylethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylether, 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- ( Diamines such as 4-aminophenyl) -1-methylethyl] benzene and 1,3-bis [1- (4- (aminophenyl) -1-methylethyl] benzene;

Imidazoles such as imidazole, benzimidazole, 4-methylimidazole and 4-methyl-2-phenylimidazole;

Pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, 2-methyl-4-phenylpyridine, nicotine, nicotinic acid, nicotinic acid amide, quinoline, Pyridines such as 4-hydroxyquinoline, 8-oxyquinoline, and acridine; In addition to piperazine, such as piperazine and 1- (2'-hydroxyethyl) piperazine,

Pyrazine, pyrazole, pyridazine, quinozaline, purine, pyrrolidine, piperidine, morpholine, 4-methylmorpholine, 1,4-dimethylpiperazine, 1,4-diazabicyclo [2.2.2] Other nitrogen-containing heterocyclic compounds such as octane

Etc. can be mentioned.

Among these basic catalysts, triethyleneamine, tri-n-propylamine, tri-n-butylamine, pyridine and the like are preferable.

The said basic catalyst can be used individually or in mixture of 2 or more types. The usage-amount of a basic catalyst is 0.01-10,000 weight part normally with respect to 100 weight part of total amounts of a silane compound.

In addition, as a solvent used for polycondensation, for example,

2-butanone, 2-pentanone, 3-methyl-2-butanone, 2-hexanone, 4-methyl-2-pentanone, 3-methyl-2-pentanone, 3,3-dimethyl-2- Linear or branched ketones such as butanone, 2-heptanone and 2-octanone;

Cyclic ketones such as cyclopentanone, 3-methylcyclopentanone, cyclohexanone, 2-methylcyclohexanone, 2, 6-dimethylcyclohexanone and isophorone;

Propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate, propylene glycol mono-i-propyl ether acetate, propylene glycol mono-n-butyl ether acetate, propylene glycol mono-i- Propylene glycol monoalkyl ether acetates such as butyl ether acetate, propylene glycol mono-sec-butyl ether acetate, and propylene glycol mono-t-butyl ether acetate;

2-Hydroxypropionate, 2-hydroxyethyl propionate, 2-hydroxypropionic acid n-propyl, 2-hydroxypropionic acid i-propyl, 2-hydroxypropionic acid n-butyl, 2-hydroxypropionic acid i-butyl, 2-hydroxypropionic acid alkyls, such as 2-hydroxypropionic acid sec-butyl and 2-hydroxypropionic acid t-butyl;

Alkyl 3-alkoxypropionates such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate and ethyl 3-ethoxypropionate;

Ethanol, n-propanol, i-propanol, n-butanol, t-butanol, cyclohexanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl Alcohols such as ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and propylene glycol mono-n-propyl ether;

Dialkylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol di-n-propyl ether and diethylene glycol di-n-butyl ether;

Ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, and ethylene glycol mono-n-propyl ether 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-methoxybutylpropionate, 3-methyl-3-methoxybutylbutylate, ethyl acetate, n-propyl acetate, n-butyl acetate, methyl acetoacetate, ethyl acetoacetate, methyl pyruvate, pyruvic acid In addition to other esters such as ethyl,

N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, benzyl ethyl ether, di-n-hexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, capronic 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 solvent can be used individually or in mixture of 2 or more types.

The amount of the solvent used is usually 2,000 parts by weight or less based on 100 parts by weight of the total amount of the silane compound.

The polycondensation for producing polysiloxane (1) and polysiloxane (1-1) is solventless or 2-butanone, 2-pentanone, 3-methyl-2-butanone, 2-hexanone, 4-methyl 2-pentanone, 3-methyl-2-pentanone, 3,3-dimethyl-2-butanone, 2-heptanone, 2-octanone, cyclopentanone, 3-methylcyclopentanone, cyclohexanone 2-methylcyclohexanone, 2,6-dimethylcyclohexanone, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol di-n-propyl ether, diethylene glycol di-n-butyl ether, It is preferable to carry out in solvents, such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, and ethylene glycol mono-n-propyl ether acetate.

In addition, during polycondensation, water may be added to the reaction system. The addition amount of water in this case is 10,000 weight part or less normally with respect to 100 weight part of total amounts of a silane compound. The reaction conditions in the reaction under polycondensation under acidic conditions or under basic conditions and under basic conditions, the reaction temperature is usually -50 to +300 ℃, preferably 20 to 100 ℃, the reaction time is usually 1 minute It is about 100 hours.

Radiation  Resin composition

The radiation sensitive resin composition of this invention contains (A) polysiloxane (1) and (B) radiation sensitive acid generator (henceforth "acid generator (B)").

Moreover, as a specific aspect of the radiation sensitive resin composition of this invention, (A) polysiloxane (1) has polysiloxane (1), structural unit (1), and structure which have a structural unit (1) and a structural unit (3). The composition which is polysiloxane (1) which has a unit (2), or polysiloxane (1) which has a structural unit (1), a structural unit (2), and a structural unit (3) is mentioned.

In the radiation sensitive resin composition of this invention, polysiloxane (1) can be used individually or in mixture of 2 or more types.

Moreover, in the radiation sensitive resin composition of this invention, one or more types of other polysiloxane can also be used together with polysiloxane (1).

As said other polysiloxane, the polysiloxane etc. which have 1 or more types of structural units represented by the said Formula (3), (4) or (5) are mentioned, for example.

Acid Generator (B)

An acid generator (B) is a component which generates an acid by exposure, and dissociates the acid dissociable group which exists in polysiloxane (1) by the action of the acid, As a result, the exposed part of a resist film is soluble in an alkaline developing solution. It has a function of forming a positive resist pattern.

The acid generator (B) is not particularly limited as long as it has the above action, but as a preferable acid generator (B), a compound which generates sulfonic acid or carboxylic acid by exposure (hereinafter referred to as "acid generator (B1) ) ") Is preferably included.

As sulfonic acid or carboxylic acid which generate | occur | produce from an acid generator (B1), the thing of Unexamined-Japanese-Patent No. 2002-220471 is mentioned, More specifically, a methyl group, an 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; Trifluoromethyl 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 group; Groups derived from norbornane, dinorbornane, adamantane or camphor; And sulfonic acids or carboxylic acids having substituted derivatives of these groups.

Examples of the acid generator (B1) include onium salt compounds for generating the sulfonic acid or carboxylic acid, sulfone compounds for generating the sulfonic acid, sulfonic acid compounds for generating the sulfonic acid, oxime compounds for generating the sulfonic acid, and the like. A carboxylic acid compound which produces | generates a carboxylic acid, the said sulfonic acid or the diazo ketone compound which produces | generates a carboxylic acid, the halogen containing compound which produces | generates the said sulfonic acid or carboxylic acid, etc. are mentioned. Examples of the onium salt compound include iodonium salts and sulfonium salts (including tetrahydrothiophenium salts), and more specifically, diphenyl iodonium salt, dinaphthyl iodonium salt, and tri Phenylsulfonium salt, trinaphthylsulfonium salt, diphenylmethylsulfonium salt, dicyclohexyl 2-oxocyclohexylsulfonium salt, 2-oxocyclohexyldimethylsulfonium salt, phenyl benzyl methylsulfonium salt, 1-naphthyl Dimethylsulfonium salt, 1-naphthyldiethylsulfonium salt, 1- (naphthalen-1-yl) tetrahydrothiophenium salt, and these groups are 1 type of substituents, such as a hydroxyl group, an alkyl group, an alkoxyl group, a cyano group, and a nitro group Or derivatives substituted with one or more of them.

Moreover, as said sulfone compound, (beta) -keto sulfones, (beta) -sulfonyl sulfones, the (alpha)-diazo compound of these compounds, etc. are mentioned, for example.

Moreover, as said sulfonic acid compound, sulfonic acid ester, sulfonic acid imide, aryl sulfonic acid ester, imino sulfonate, etc. are mentioned, for example.

Moreover, as said oxime compound, an aryl group containing oxime sulfonic acid is mentioned, for example.

Moreover, as said carboxylic acid compound, carboxylic acid ester, carboxylic acid imide, carboxylic acid cyanate etc. are mentioned, for example.

Moreover, as said diazo ketone compound, a 1, 3- diketo-2- diazo compound, a diazo benzoquinone compound, a diazonaphthoquinone compound etc. are mentioned, for example.

Moreover, as said halogen containing compound, a haloalkyl group containing hydrocarbon compound, a haloalkyl group containing heterocyclic compound, etc. are mentioned, for example.

In this invention, an acid generator (B) can be used individually or in mixture of 2 or more types, and can also use 2 or more types of acid generator (B1) which produces a different sulfonic acid together, and uses different car 2 or more types of acid generator (B1) which generates an acid can be used together, or 1 or more types of acid generators (B1) which generate a sulfonic acid, and an acid generator (B1) which generate a carboxylic acid can be used. It can be used in combination of 1 or more type.

The use amount of the acid generator (B) is usually 0.1 to 30 parts by weight, preferably 0.5 to 20 parts by weight with respect to 100 parts by weight of all polysiloxane components from the viewpoint of securing the sensitivity and developability as a resist. In this case, when the usage-amount of an acid generator (B) is less than 0.1 weight part, there exists a tendency for a sensitivity and developability to fall, and when it exceeds 30 weight part, transparency to radiation falls and a rectangular resist pattern is obtained. It tends to be difficult.

-additive-

Various additives, such as an acid diffusion control agent, a dissolution control agent, and surfactant, can be mix | blended with the radiation sensitive resin composition of this invention.

The acid diffusion control agent is a component having the effect of controlling the diffusion phenomenon of the acid generated from the acid generator by exposure in the resist film and suppressing an undesired chemical reaction in the non-exposed region.

By incorporating such an acid diffusion control agent, the storage stability of the resulting radiation-sensitive resin composition is further improved, and the resolution as a resist is further improved, and the inch time from exposure to development treatment (PED) The variation in the line width of the resist pattern due to the variation of can be suppressed, and a composition having excellent process stability can be obtained.

As the acid diffusion control agent, a nitrogen-containing organic compound in which basicity does not change by exposure or heat treatment in the formation process of a resist pattern is preferable.

As such a nitrogen-containing organic compound, the compound (henceforth "acid diffusion control agent (C)") represented by following General formula (10) is mentioned, for example.

In formula (10), each R ⁵ independently represents a hydrogen atom, a straight chain, a branched or cyclic alkyl group, an aryl group or an aralkyl group, and these alkyl groups, aryl groups and aralkyl groups may be substituted with functional groups such as hydroxyl groups. And U ¹ represents a divalent organic group, and s is an integer of 0 to 2.]

In an acid diffusion control agent (C), the compound whose s = 0 is called "acid diffusion control agent (C1)", and the compound whose s = 1-2 is called "acid diffusion control agent (C2)". Moreover, the polyamino compound and polymer which have three or more nitrogen atoms together are called "acid diffusion control agent (C3)."

Examples of nitrogen-containing organic compounds other than the acid diffusion control agent (C) include quaternary ammonium hydroxide compounds, amide group-containing compounds, urea compounds, nitrogen-containing heterocyclic compounds, and the like.

Examples of the acid diffusion control agent (C1) include mono (cyclo) alkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine and cyclohexylamine; Di-n-butylamine, di-n-pentylamine, di-n-hexylamine, di-n-heptylamine, di-n-octylamine, di-n-nonylamine, di-n-decylamine, cyclo Di (cyclo) alkylamines such as hexylmethylamine and dicyclohexylamine; Triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, tri-n- Tri (cyclo) alkylamines such as nonylamine, tri-n-decylamine, cyclohexyldimethylamine, dicyclohexylmethylamine, tricyclohexylamine; Aniline, N-methylaniline, N, N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, 4-nitroaniline, 2,6-dimethylaniline, 2,6-diisopropylaniline, Aromatic amines, such as diphenylamine, triphenylamine, and naphthylamine, are mentioned.

As the acid diffusion control agent (C2), for example, 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 '-Diaminodiphenylether, 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-methylethyl] benzene, bis (2-dimethyl Aminoethyl) ether, bis (2-diethylaminoethyl) ether, and the like.

As an acid diffusion control agent (C3), the polymer of polyethyleneimine, polyallylamine, 2-dimethylaminoethyl acrylamide, etc. are mentioned, for example.

As said quaternary ammonium hydroxide compound, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-propylammonium hydroxide, tetra-n-butylammonium hydroxide, etc. are mentioned, for example. Can be.

As said amide group containing compound, Nt-butoxycarbonyldi-n-octylamine, Nt-butoxycarbonyldi-n-nonylamine, Nt-butoxycarbonyldi-n-decylamine, 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'-dia Minodiphenylphenylmethane, N, N'-di-t-butoxycarbonylhexamethylenediamine, N, N, N ', N'-tetra-t-butoxycarbonylhexamethylenediamine, N, N'-di -t-butoxycarbonyl-1,7-diaminoheptane, N, N'-di-t-butoxycarbonyl-1,8-diaminooctane, N, N'-di-t-butoxycar Bonyl-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'-diamino Nt-butoxycarbonyl group containing amino compounds, such as phenylmethane, Nt-butoxycarbonyl benzimidazole, Nt-butoxycarbonyl-2-methylbenzimidazole, and Nt-butoxycarbonyl-2-phenylbenzimidazole Besides, formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide, pyrrolidone, N-methylpy A ralidone etc. are mentioned.

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-butylthiourea etc. are mentioned.

As said nitrogen-containing heterocyclic compound, for example, imidazole, 4-methylimidazole, 1-benzyl-2-methylimidazole, 4-methyl-2-phenylimidazole, benzimidazole, 2- Imidazoles such as phenylbenzimidazole; Pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, 2-methyl-4-phenylpyridine, nicotine, nicotinic acid, nicotinic acid amide, quinoline, Pyridines such as 4-hydroxyquinoline, 8-oxyquinoline, and acridine; In addition to piperazines such as piperazine and 1- (2-hydroxyethyl) piperazine, pyrazine, pyrazole, pyridazine, quinozaline, purine, pyrrolidine, piperidine, 3-piperidino-1, 2-propanediol, morpholine, 4-methylmorpholine, 1, 4- dimethyl piperazine, 1, 4- diazabicyclo [2.2.2] octane, etc. are mentioned.

These acid diffusion control agents can be used individually or in mixture of 2 or more types.

The compounding quantity of an acid diffusion control agent is 100 mol% or less normally with respect to an acid generator (B), Preferably it is 50 mol% or less, More preferably, it is 30 mol% or less. In this case, when the compounding quantity of an acid diffusion control agent exceeds 100 mol%, there exists a tendency for the sensitivity as a resist and the developability of an exposure part to fall. Moreover, when the compounding quantity of an acid diffusion control agent is less than 0.1 mol%, there exists a possibility that pattern shape and dimensional fidelity as a resist may fall depending on process conditions.

Moreover, as said dissolution control agent, the compound etc. which have an effect which controls the dissolution contrast and / or dissolution rate at the time of using a resist are mentioned, for example.

In this invention, the compounding quantity of a dissolution control agent is 50 weight part or less normally, Preferably it is 30 weight part or less with respect to 100 weight part of all polysiloxane components. In this case, when the compounding quantity of a dissolution control agent exceeds 50 weight part, there exists a tendency for the heat resistance as a resist to fall.

Moreover, the said surfactant is a component which shows the effect | action which improves applicability | paintability, striation, developability, etc ..

As such a surfactant, For example, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene n-octyl phenyl ether, polyoxyethylene n-nonylphenyl ether, In addition to nonionic surfactants such as polyethylene glycol dilaurate and polyethylene glycol distearate, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 75, and Copper No. 95 (Tomosakaesha Co., Ltd.) Kagaku Co., Ltd., F-Top EF301, Copper EF303, Copper EF352 (Tochem Products Co., Ltd.), Megafax F171, Copper F173 (manufactured by Dainippon Ink & Chemical Co., Ltd.), Florad FC430, Copper FC431 (manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard AG710, Suplon S-382, East SC-101, East SC-102, East SC-103, East SC-104, East SC-105, East SC-106 ( Asahi Glass Co., Ltd.) etc. are mentioned.

These surfactant can be used individually or in mixture of 2 or more types.

The compounding quantity of surfactant is 2 weight part or less normally with respect to 100 weight part of all polysiloxane components.

Moreover, as an additive of that excepting the above, an antihalation agent, an adhesion | attachment adjuvant, a storage stabilizer, an antifoamer, etc. are mentioned.

Preparation of composition solution

In the radiation sensitive resin composition of this invention, after melt | dissolving in a solvent so that the total solid concentration may be 1-25 weight% normally, Preferably it is 2-15 weight% normally at the time of the use, For example, For example, a pore size of 0.2 It is prepared as a composition solution by filtration with a filter of about μm.

As a solvent used for preparation of the said composition solution, for example,

2-butanone, 2-pentanone, 3-methyl-2-butanone, 2-hexanone, 4-methyl-2-pentanone, 3-methyl-2-pentanone, 3,3-dimethyl-2- Linear or branched ketones such as butanone, 2-heptanone and 2-octanone;

Cyclic ketones such as cyclopentanone, 3-methylcyclopentanone, cyclohexanone, 2-methylcyclohexanone, 2,6-dimethylcyclohexanone and isophorone;

Propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate, propylene glycol mono-i-propyl ether acetate, propylene glycol mono-n-butyl ether acetate, propylene glycol mono-i- Propylene glycol monoalkyl ether acetates such as butyl ether acetate, propylene glycol mono-sec-butyl ether acetate, and propylene glycol mono-t-butyl ether acetate;

2-Hydroxypropionate, 2-hydroxyethyl propionate, 2-hydroxypropionic acid n-propyl, 2-hydroxypropionic acid i-propyl, 2-hydroxypropionic acid n-butyl, 2-hydroxypropionic acid i-butyl, 2-hydroxypropionic acid alkyls, such as 2-hydroxypropionic acid sec-butyl and 2-hydroxypropionic acid t-butyl;

Alkyl 3-alkoxypropionates such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate and ethyl 3-ethoxypropionate;

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-octa Fluoro-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-perfluoro nonan-1,2-diol, 1H, 1H Fluorine-containing alcohols such as 2H, 2H-perfluoro-1-decanol, 1H, 1H, 2H, 3H, and 3H-perfluorodecane-1,2-diol;

2,2,2-trifluoroethylbutyrate, ethylheptafluorobutylate, ethyl heptafluorobutyl acetate, hexafluoroglutarate, ethyl-3-hydroxy-4,4,4-trifluoro Butylate, ethyl-2-methyl-4,4,4-trifluoroacetoacetate, ethyl pentafluorobenzoate, ethyl pentafluoropropionate, ethyl pentafluoropropionate, ethylperfluorooctanoate, Ethyl-4,4,4-trifluoroacetoacetate, ethyl-4,4,4-trifluorobutylate, ethyl-4,4,4-trifluorocrotonate, ethyltrifluorosulfonate, ethyl -3- (trifluoromethyl) butylate, ethyltrifluoropyruvate, ethyltrifluoroacetate, isopropyl-4,4,4-trifluoroacetoacetate, methylperfluorodecanoate, methyl purple Luoro (2-methyl-3-oxahexanoate), methylperfluorononanoe , Methylperfluorooctanoate, 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, trifluoromethyl acetate n-butyl, 3-trifluorome Fluorine-containing esters such as methyl oxypropionate, 1,1,1-trifluoro-2-propyl acetate, and 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, trifluoroacetoaldehydeethylhemiacetal, 2H-perfluoro (5-methyl-3,6-dioxanonan), 2H-perfluoro (5,8,11,14-tetramethyl-3,6,9,12,15-pentaoxaoctadecane), (perfluoro-n-butyl) tetrahydrofuran, perfluoro (n-butyltetrahydro Fluorine-containing ethers such as furan) and propylene glycol trifluoromethyl ether;

2,4-difluoropropiophene, 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, perfluoro Fluorine-containing ketones such as cyclohexanone;

Fluorine-containing amines such as trifluoroacetoamide, perfluorotributylamine, perfluorotrihexylamine, perfluorotripentylamine, and perfluorotripropylamine;

Fluorine-substituted cyclic hydrocarbons such as 2,4-difluorotoluene, perfluorodecarin, perfluoro (1,2-dimethylcyclohexane) and perfluoro (1,3-dimethylcyclohexane)

In addition to fluorine-containing solvents such as

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, 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy-3-methylbutyrate, 3-methoxybutyl acetate, 3-methyl-3- Methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, 3-methyl-3-methoxybutylbutylate, 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, capronic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate Etc. can be mentioned.

These solvents can be used individually or in mixture of 2 or more types. In particular, linear or branched ketones, cyclic ketones, propylene glycol monoalkyl ether acetates, alkyl 2-hydroxypropionates, alkyl 3-alkoxypropionates, fluorine-containing solvents and the like are preferable.

Formation method of resist pattern

In the radiation-sensitive resin composition of the present invention, an acid is generated from an acid generator by exposure, and by the action of the acid, the acid dissociable group in the polysiloxane (1) dissociates to generate a carboxyl group, and as a result, exposure of the resist The solubility with respect to a negative alkali developing solution becomes high, the said exposure part melt | dissolves and removes with an alkaline developing solution, and a positive resist pattern is obtained.

When forming a resist pattern from the radiation sensitive resin composition of this invention, the composition solution is, for example, a wafer coated with a silicon wafer, aluminum, or the like by appropriate coating means such as spin coating, cast coating or roll coating, A resist film is formed by apply | coating on the board | substrate etc. in which the lower layer film was previously formed, and after heat-processing (henceforth "PB") in advance if necessary, it exposes to the said resist film so that a predetermined | prescribed resist pattern may be formed. . As radiation used at this time, far ultraviolet rays, electron beams, X-rays, etc. which are represented by an F2 excimer laser (wavelength 157 nm) or an ArF excimer laser (wavelength 193 nm) are preferable.

In this invention, it is preferable to perform heat processing (henceforth "PEB") after exposure. By this PEB, the dissociation reaction of the acid dissociable group in the polysiloxane (1) proceeds smoothly. Although the heating conditions of PEB vary with the compounding composition of a resist composition, it is 30-200 degreeC normally, Preferably it is 50-170 degreeC.

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 (see, for example, Japanese Patent Application Laid-Open No. 6-12452). Moreover, in order to prevent the influence of basic impurities etc. contained in an environmental atmosphere, a protective film can also be formed on a resist film (for example, refer Unexamined-Japanese-Patent No. 5-188598), or use these techniques together You may.

Next, by developing the exposed resist film, a predetermined resist pattern is formed.

As a developing solution used for image development, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia water, 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 An alkaline aqueous solution which melt | dissolved at least 1 sort (s) of alkaline compounds, such as -diazabicyclo- [4.3.0] -5-nonene, is preferable.

The concentration of the alkaline aqueous solution is usually 10% by weight or less. In this case, when the density | concentration of alkaline aqueous solution exceeds 10 weight%, there exists a possibility that a non-exposure part may also melt | dissolve in a developing solution, and it is unpreferable.

Moreover, an organic solvent can also be added to the developing solution containing the said alkaline aqueous solution, for example.

Examples of the organic solvent include acetone, 2-butanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, 3-methylcyclopentanone, and 2,6-dimethylcyclohexanone. Ketones; Methyl alcohol, ethyl alcohol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, t-butyl alcohol, cyclopentanol, cyclohexanol, 1,4-hexanediol, 1,4-hexanedimethylol Alcohols; 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, a phenol, acetonyl acetone, dimethylformamide, etc. are mentioned.

These organic solvents can be used individually or in mixture of 2 or more types.

As for the usage-amount of an organic solvent, 100 weight% or less is preferable with respect to alkaline aqueous solution. In this case, when the usage-amount of an organic solvent exceeds 100 volume%, developability will fall and there exists a possibility that the image development residual part of an exposure part may increase.

In addition, an appropriate amount of a surfactant may be added to the developing solution containing an alkaline aqueous solution.

In addition, after developing with a developing solution containing an alkaline aqueous solution, it is generally washed with water and dried.

Hereinafter, an Example is given and embodiment of this invention is described further more concretely. However, this invention is not restrict | limited to these Examples at all.

Mw:

As for Mw of the polysiloxane obtained by each Example and comparative example which are mentioned below, and the polymer obtained by the preparation example mentioned below, the flow rate is 1.0 ml using the GPC column (2 G2000HXL, 1 G3000HXL, 1 G4000HXL) by the Toso Corporation make. It measured by gel permeation chromatography (GPC) which makes monodisperse polystyrene the standard on the analysis conditions of / min, an elution solvent tetrahydrofuran, and column temperature 40 degreeC.

Synthesis Example 1 (Synthesis of Silane Compound (I))

To three flasks equipped with a stirrer, a reflux condenser, and a thermometer, 220 g of triethoxysilane and 198 g of 5- (1-methylcyclopentyl) oxycarbonylbicyclo [2.2.1] hepto-2-ene were added at room temperature. After stirring, 1 ml of 0.2 mol i-propyl alcohol solution of chloroplatinic acid (H 2 PtCl 6) was added to initiate the reaction, and heated at 100 ° C. for 30 hours, followed by further 0.2 mol i-propyl alcohol solution of chloroplatinic acid 1 ML was added and heated at 100 ° C. for 5 hours. Thereafter, the reaction solution was returned to room temperature, diluted with n-hexane, filtered through a suction funnel covered with celite, and the obtained filtrate was distilled off under reduced pressure to obtain a crude product. Then, the crude product was refine | purified by distillation under reduced pressure, and the compound 262g was obtained as a residual of 137 degreeC by the boiling point in 0.06mmHg.

As a result of measuring <^1> H-NMR spectrum (chemical shift (delta)) about this compound, it is as follows, and is represented by said Formula (I-1-1) (henceforth "a compound (a-1)"). Was identified as.

δ in ppm:

3.8 (CH2 group in ethoxy group), 2.7-1.3 (CH group in norbornane ring, CH2 group in norbornane ring, CH3 group, CH2 group in cyclohexane ring), 1.2 (ethoxy group).

Synthesis Example 2

5- (1-ethylcyclopentyl) oxycarbonylbicyclo [2.2.1] hepto-2- instead of 5- (1-methylcyclopentyl) oxycarbonylbicyclo [2.2.1] hepto-2-ene Using the yen, in accordance with the method of Synthesis Example 1, a compound represented by the formula (I-1-2) was obtained.

Synthesis Example 3

5- (1-ethylcyclopentyl) oxycarbonylbicyclo [2.2.1] hepto-2- instead of 5- (1-methylcyclopentyl) oxycarbonylbicyclo [2.2.1] hepto-2-ene Using the yen, in accordance with the method of Synthesis Example 1, a compound represented by the formula (I-1-4) was obtained.

Example 1 (Preparation of Polysiloxane (1))

Into three flasks equipped with a stirrer, a reflux condenser and a thermometer, 36.3 g of a compound (a-1) and a silane compound represented by the following formula (b-1) (hereinafter referred to as "compound (b-1)") 41.32 g, a silane compound represented by the following formula (b-2) (hereinafter referred to as "compound (b-2)") 22.39 g, 4-methyl-2-pentanone 100 g, and 1.75 wt% oxalic acid aqueous solution were added thereto. It was made to react at 60 degreeC for 6 hours, stirring. The reaction vessel was then cooled with water to stop the reaction.

Subsequently, 34.0 g of distilled water and 47.7 g of triethylamine were added to the reaction solution, the mixture was stirred at 80 ° C for 6 hours in a nitrogen stream, followed by water cooling, and further stirred by adding an aqueous solution of 35.9 g of oxalic acid dissolved in 476.5 g of distilled water. Thereafter, the reaction solution was transferred to a separatory funnel, the water layer was discarded, water was further added with ion-exchanged water, and water washing was repeated until the reaction solution became neutral. Then, the organic layer was distilled off under reduced pressure and 62.1 g of polysiloxane (1) was obtained. Mw of the obtained polysiloxane (1) was 1,740.

Example 2 (Preparation of Polysiloxane (1))

In three flasks equipped with a stirrer, a reflux condenser and a thermometer, 22.27 g of a compound (a-1) and a silane compound of 42.36 g of a silane compound represented by the following formula (b-3) and a silane compound represented by the following formula (b-4) 19.77 g, 4-methyl-2-pentanone 100 g, and 14.1 g of an aqueous solution of 1.75 wt% oxalic acid were added thereto, and the mixture was reacted at 60 ° C. for 6 hours. The reaction vessel was then cooled with water to stop the reaction.

Subsequently, 21.4 g of distilled water and 29.3 g of triethylamine were added to the reaction solution, the mixture was stirred at 80 ° C. for 6 hours in a nitrogen stream, followed by water cooling, and further stirred by adding an aqueous solution in which 22.0 g of oxalic acid was dissolved in 292.4 g of distilled water. Thereafter, the reaction solution was transferred to a separatory funnel, the water layer was discarded, water was further added with ion-exchanged water, and water washing was repeated until the reaction solution became neutral. Then, the organic layer was distilled off under reduced pressure and 74.2 g of polysiloxane (1) was obtained. Mw of the obtained polysiloxane (1) was 2,060.

Example 3 (Preparation of Polysiloxane (1))

In three flasks equipped with a stirrer, a reflux condenser and a thermometer, 48.08 g of compound (a-1), 51.92 g of compound (b-1), 100 g of 4-methyl-2-pentanone, and 30.53 g of an aqueous solution of 1.75 wt% oxalic acid were added. It was made to react at 60 degreeC for 6 hours, stirring. The reaction vessel was then cooled with water to stop the reaction.

Subsequently, the reaction solution was transferred to a separatory funnel, the water layer was discarded, water was further washed with addition of ion-exchanged water, and water washing was repeated until the reaction solution became neutral. Then, the organic layer was distilled off under reduced pressure and 51.1 g of polysiloxane (1) was obtained. Mw of the obtained polysiloxane (1) was 1,530.

Example 4 (Preparation of Polysiloxane (1))

In three flasks equipped with a stirrer, a reflux condenser and a thermometer, 31.35 g of compound (a-1), 17.85 g of compound (b-1), 50.79 g of compound (b-2), and 100 g of 4-methyl-2-pentanone 29.86 g of an aqueous 1.75 wt% oxalic acid solution was added thereto and reacted at 60 ° C. for 6 hours while stirring. The reaction vessel was then cooled with water to stop the reaction.

Subsequently, 44.1 g of distilled water and 61.9 g of triethylamine were added to the reaction solution, the mixture was stirred at 40 ° C. for 6 hours in a nitrogen stream, followed by water cooling, and further stirred by adding an aqueous solution in which 46.5 g of oxalic acid was dissolved in 617.6 g of distilled water. Thereafter, the reaction solution was transferred to a separatory funnel, the water layer was discarded, water was further added with ion-exchanged water, and water washing was repeated until the reaction solution became neutral. Thereafter, the organic layer was distilled off under reduced pressure to obtain 63.1 g of polysiloxane (1). Mw of the obtained polysiloxane (1) was 2,540.

Comparative Example 1 (Preparation of Polysiloxane for Comparison)

In three flasks equipped with a stirrer, a reflux condenser and a thermometer, 34.68 g of the silane compound represented by the following formula (r-1), 42.36 g of the following formula (b-1), 22.96 g of the following formula (b-2), 4 100 g of methyl-2-pentanone and 23.6 g of an aqueous solution of 1.75 wt% oxalic acid were added and reacted at 60 ° C for 6 hours while stirring. The reaction vessel was then cooled with water to stop the reaction.

Subsequently, 34.9 g of distilled water and 48.9 g of triethylamine were added to the reaction solution, the mixture was stirred at 80 ° C for 6 hours in a nitrogen stream, followed by water cooling, and further stirred by adding an aqueous solution of 36.8 g of oxalic acid dissolved in 488.5 g of distilled water. Thereafter, the reaction solution was transferred to a separatory funnel, the water layer was discarded, water was further added with ion-exchanged water, and water washing was repeated until the reaction solution became neutral. Thereafter, the organic layer was distilled off under reduced pressure to obtain 60.9 g of polysiloxane. Mw of this polysiloxane was 1,910.

Preparation example (preparation of composition for lower layer film formation)

100 parts by weight of acenaphthalene, 78 parts by weight of toluene, 52 parts by weight of dioxane and 3 parts by weight of azobisisobutyronitrile were placed in a separating flask equipped with a thermometer under a nitrogen atmosphere, followed by stirring at 70 ° C for 5 hours. Thereafter, 5.2 parts by weight of p-toluenesulfonic acid monohydrate and 40 parts by weight of paraformaldehyde were added, and the temperature was raised to 120 ° C, followed by further stirring for 6 hours. Thereafter, the reaction solution was poured into a large amount of i-propyl alcohol, the precipitated polymer was separated by filtration, and dried under reduced pressure at 40 ° C to obtain a polymer having a Mw of 22,000.

Subsequently, 10 parts by weight of the obtained polymer, 0.5 parts by weight of bis (4-t-butylphenyl) iodonium 10-camphor-sulfonate, 4,4 '-[1- {4- (1- [4-hydroxyphenyl] 0.5 weight part of 1-methylethyl) phenyl} ethylidene] bisphenol was melt | dissolved 89 weight part of cyclohexanone, and the obtained solution was filtered through the membrane filter of 0.1 micrometer of pore diameters, and the composition for lower layer film formation was prepared.

Evaluation Examples 1 to 5 and Comparative Evaluation Example 1 (Evaluation of the radiation sensitive resin composition)

8 moles with respect to the total amount of each 100 parts of polysiloxane shown in Table 1 (it is based on a weight. The same applies below), 900 parts of 2-heptanone, the acid generator (B) shown in Table 1, and an acid generator (B). % 2-phenylbenzimidazole was uniformly mixed to prepare a composition solution.

Subsequently, each composition solution was applied onto the substrate on which the underlayer film was previously formed on the surface of the silicon wafer by spin coating, and then subjected to PB for 90 seconds on a hot plate kept at 100 ° C to form a resist film having a film thickness of 1,500 Pa. Formed.

Here, the underlayer film is formed by baking the underlayer film-forming composition on a silicon wafer by spin coating, and then baking on a hot plate at 180 ° C. for 60 seconds and further at 300 ° C. for 120 seconds to form a film thickness of 3,000 kPa. It's just that.

Subsequently, the exposure amount was made to each resist film using the ArF excimer laser (wavelength 193 nm, NA = 0.78, (sigma) = 0.85) using ArF exposure apparatus S306C (brand name) by Nikon Corporation, and a photo exposure amount. It changed and exposed, and PEB was performed for 90 second on the hotplate maintained at 80 degreeC or 95 degreeC. Then, after developing at 23 degreeC for 60 second with 2.38 weight% of tetramethylammonium hydroxide aqueous solution, it washed with water and dried and formed the positive resist pattern.

Next, the line and space pattern was evaluated by the following method. The evaluation results are shown in Table 2.

Evaluation of the Line and Space Pattern

The exposure amount which forms the line-and-space pattern 1L1S with a line line width of 100 nm with a line width of 1: 1 was made into the optimal exposure amount, and this optimal exposure amount was made into the sensitivity (1L1S).

In addition, the line width (CD) of the line pattern when one line 5 space (1L5S) having a line line width of 180 nm was formed at this optimum exposure amount. The larger the CD value, the better the I-D bias.

In Table 1, the acid generator (B) is as follows.

Acid Generator (B):

B-1: triphenylsulfonium nonafluoro-n-butanesulfonate

B-2: triphenylsulfonium 2-norbornyl-1,1,2,2-tetrafluoroethane-1-sulfonate

B-3: bis (t-butylphenyl) iodonium nonafluoro-n-butanesulfonate

B-4: bis (cyclohexylsulfonyl) diazomethane

B-5: triphenylsulfonium 10-camphorsulfonate

Polysiloxane (100 parts) Acid generator (B) (part) PEB temperature (℃) Sensitivity (1L1S) (J / ㎡) CD value (nm) Evaluation example 1 Example 1 B-1 (5) B-5 (1.5) 80 210 133 Evaluation example 2 Example 1 B-2 (5) B-5 (1.5) 80 230 139 Evaluation Example 3 Example 1 B-3 (5) B-5 (1.5) 80 370 140 Evaluation example 4 Example 1 B-3 (5) B-4 (1.5) B-5 (1.5) 80 300 138 Evaluation example 5 Example 2 B-3 (5) B-5 (1.5) 80 400 140 Comparative Example 1 Comparative Example 1 B-3 (5) B-5 (1.5) 95 380 121

Evaluation Examples 6 to 7 and Comparative Evaluation Example 2 (evaluation of radiation-sensitive resin composition)

8 moles with respect to the total amount of each 100 parts of polysiloxane shown in Table 2 (it is based on a weight. The same applies below), 900 parts of 2-heptanone, the acid generator (B) shown in Table 2, and an acid generator (B). % 2-phenylbenzimidazole was uniformly mixed to prepare a composition solution.

Next, in the same manner as in Evaluation Examples 1 to 5 and Comparative Evaluation Example 2, a positive resist pattern was formed.

Moreover, the board | substrate for image development defect inspection was produced as follows. That is, after apply | coating each composition solution so that a dry film thickness may be set to 150 nm on the board | substrate which previously formed the anti-reflective film ARC 29A (brand name, manufactured by Nissan Kagaku Co., Ltd.) with a film thickness of 77 nm on the silicon wafer surface, PB was performed at 140 degreeC for 90 second, and the resist film was formed. Subsequently, using the ArF excimer laser (wavelength 193 nm, NA = 0.78, sigma = 0.85) using the ArF exposure apparatus S306C (brand name) by Nikon Corporation for each resist film, the pore size 110 It exposed and formed so that the contact hole of nm may be formed in the pitch of 300 nm, and PEB was performed for 90 second on the hotplate hold | maintained at 140 degreeC. Then, it developed with 2.38 weight% of tetramethylammonium hydroxide aqueous solution at 23 degreeC for 60 second, washed with water, and dried, and obtained the board | substrate for image development defect inspection. At this time, application | coating, PB, PEB, and image development of the composition solution were performed inline using Tokyo Electron Co., Ltd. product ACT8 (brand name).

Subsequently, evaluation was made about the line-and-space pattern and the contact hole pattern, and the number of image development defects was evaluated as the following method. The evaluation results are shown in Table 2.

Evaluation of the Line and Space Pattern

The cross-sectional shape of the line pattern of the formed line and space pattern (1L1S) of 100 nm of line | wire line widths was observed and evaluated by the scanning electron microscope.

Evaluation of Contact Hole Patterns

The exposure amount which forms the hole-and-space pattern 1H1S of a contact hole diameter of 100 nm in the line width of 1: 1 was made into the optimal exposure amount, and this optimal exposure amount was made into the sensitivity (1H1S).

In addition, when the focus is shifted out of the optimum exposure dose to form a hole-and-space pattern 1H1S having a contact hole diameter of 100 nm, the focal depth at which the contact hole diameter is 90 nm or more and 110 nm or less is measured. It was set as (DOF (1H1S)).

Evaluation of the number of developing defects

Using the defect inspection apparatus KLA2351 (brand name) by KLA Tencor Co., Ltd., for the development defect inspection substrate, the pixel size of the defect inspection apparatus was set to 0.16 µm and the threshold value was set to 13, and measured in array mode. Developing defects were calculated by detecting the developing combination extracted from the difference caused by the comparison image and the pixel-by-pixel overlap.

In Table 2, the acid generator (B) is as follows.

Acid Generator (B):

B-1: triphenylsulfonium nonafluoro-n-butanesulfonate

B-2: triphenylsulfonium 2-norbornyl-1,1,2,2-tetrafluoroethane-1-sulfonate

Polysiloxane (100 parts) Acid generator (B) (part) PEB temperature (℃) Pattern shape Sensitivity (1H1S) (J / ㎡) DOF (1H1S) (μm) Development defect number Evaluation Example 6 Example 3 B-1 (5) B-2 (1.5) 80 Rectangle 450 0.4 35 Evaluation example 7 Example 4 B-1 (5) B-2 (1.5) 80 Rectangle 430 0.4 40 Comparative Example 2 Comparative Example 1 B-1 (5) B-2 (1.5) 95 T-Top 340 0.2 9550

Example 5 (Preparation of Polysiloxane (1-1))

In three flasks equipped with a stirrer, a reflux condenser and a thermometer, a silane compound represented by 36.3 g of a silane compound (a-1) and the following formula (a-2) (hereinafter referred to as "silane compound (a-2)") 41.3g, 22.4g of silane compound (b-1), 100g of 4-methyl-2-pentanone, and 23.0g of an aqueous 1.75% by weight oxalic acid solution were added thereto, and the mixture was reacted at 60 ° C for 6 hours. The reaction vessel was then cooled with water to stop the reaction.

Subsequently, 34.0 g of distilled water and 47.7 g of triethylamine were added to the reaction solution, the mixture was stirred at 80 ° C for 6 hours in a nitrogen stream, followed by water cooling, and further stirred by adding an aqueous solution of 35.9 g of oxalic acid dissolved in 476.5 g of distilled water. . Thereafter, the reaction solution is transferred to a separatory funnel, the water layer is discarded, water is further washed with addition of ion-exchanged water, water washing is repeated until the reaction solution becomes neutral, and the organic layer is distilled off under reduced pressure to obtain polysiloxane ( 1-1) 62.1 g was obtained. Mw of the obtained polysiloxane (1-1) was 2,140.

Example 6 (Preparation of Polysiloxane (1-1))

In three flasks equipped with a stirrer, a reflux condenser and a thermometer, 13.2 g of a silane compound (a-1) and a silane compound represented by the following formula (a-3) (hereinafter referred to as "silane compound (a-3)") ) 24.5g, 62.3g of silane compound (b-4), 100g of 4-methyl-2-pentanone, and 16.7g of 1.75 wt% aqueous oxalic acid solution were added thereto, and the mixture was reacted at 60 ° C for 6 hours. The reaction vessel was then cooled with water to stop the reaction.

Next, 24.7 g of distilled water and 34.6 g of triethylamine were added to the reaction solution, the mixture was stirred at 80 ° C. for 6 hours in a nitrogen stream, followed by water cooling, and further stirred by adding an aqueous solution in which 26.0 g of oxalic acid was dissolved in 345.7 g of distilled water. Thereafter, the reaction solution is transferred to a separatory funnel, the water layer is discarded, water is further washed with addition of ion-exchanged water, water washing is repeated until the reaction solution becomes neutral, and the organic layer is distilled off under reduced pressure to obtain polysiloxane ( 1-1) 73.5 g was obtained. Mw of the obtained polysiloxane (1-1) was 2,060.

Comparative Example 2 (Production of Comparative Polysiloxane)

In three flasks equipped with a stirrer, a reflux condenser and a thermometer, 24.6 g of the silane compound (a-3), 30.1 g of the silane compound (b-1), 45.4 g of the silane compound (b-4), 4-methyl-2- 100 g of pentanone and 16.7 g of a 1.75 wt% oxalic acid aqueous solution were added thereto, and the mixture was reacted at 60 ° C for 6 hours while stirring. The reaction vessel was then cooled with water to stop the reaction. Subsequently, 24.7 g of distilled water and 34.7 g of triethylamine were added to the reaction solution, the mixture was stirred at 80 ° C for 6 hours in a nitrogen stream, followed by water cooling, and further stirred by adding an aqueous solution in which 26.1 g of oxalic acid was dissolved in 346.2 g of distilled water. Thereafter, the reaction solution was transferred to a separatory funnel, the water layer was discarded, water was further washed with addition of ion-exchanged water, water washing was repeated until the reaction solution became neutral, and the organic layer was distilled off under reduced pressure to obtain polysiloxane 73.3. g was obtained. Mw of this polysiloxane was 2,160.

Evaluation examples 8-9 and comparative evaluation example 3 (evaluation of a radiation sensitive resin composition)

About the total amount of each 100 parts of siloxane resins shown in Table 3 (it is the same on a weight basis), 900 parts of 2-heptanone, the acid generator (B) shown in Table 1, and an acid generator (B) 8 Mole% 2-phenylbenzimidazole was uniformly mixed to prepare a composition solution.

Subsequently, each composition solution was applied onto the substrate on which the underlayer film was previously formed on the surface of the silicon wafer by spin coating, and then subjected to PB for 90 seconds on a hot plate kept at 100 ° C to form a resist film having a film thickness of 1,500 Pa. Formed. Here, the underlayer film is formed in the same manner as in the cases of Evaluation Examples 1 to 5 and Comparative Evaluation Example 1.

Subsequently, the exposure amount was made to each resist film using the ArF excimer laser (wavelength 193 nm, NA = 0.78, (sigma) = 0.85) using ArF exposure apparatus S306C (brand name) by Nikon Corporation, and a photo exposure amount. It changed and exposed, and PEB was performed for 90 second on the hotplate maintained at 100 degreeC. Then, after developing at 23 degreeC for 60 second with 2.38 weight% of tetramethylammonium hydroxide aqueous solution, it washed with water and dried and formed the positive resist pattern.

Next, the line and space pattern was evaluated by the following method. Table 3 shows the results of the evaluation.

Evaluation of the Line and Space Pattern

The exposure amount which forms the line-and-space pattern 1L1S with a line width of 90 nm at a line width of 1: 1 was set as an optimal exposure amount, and this optimum exposure amount was made into sensitivity (1L1S).

Further, by focusing at this optimum exposure amount and exposing, when the line-and-space pattern 1L1S having a line line width of 90 nm is formed, the focus range at which the line width of the line pattern is 81 nm or more and 99 nm or less is measured, and the depth of focus is determined. It was set as (DOF (1L1S)).

In Table 3, the acid generator (B) is as follows.

B-1: triphenylsulfonium nonafluoro-n-butanesulfonate

B-2: triphenylsulfonium 2-norbornyl-1,1,2,2-tetrafluoroethane-1-sulfonate

Polysiloxane (100 parts) Acid generator (B) (part) PEB temperature (℃) Sensitivity (1L1S) (J / ㎡) DOF (1L1S) (nm) Evaluation example 8 Example 5 B-1 (5) B-2 (1.5) 100 210 500 Evaluation Example 9 Example 6 B-1 (5) B-2 (1.5) 100 230 550 Comparative Evaluation Example 3 Comparative Example 2 B-1 (5) B-2 (1.5) 100 380 250

The silane compound (I) of this invention can be used especially suitably as a raw material which synthesize | combines the polysiloxane (1) of this invention.

Moreover, since the radiation sensitive resin composition of this invention which contains polysiloxane (1) as a resin component can lower PEB temperature, and can control the diffusion of the acid which generate | occur | produced by exposure, a line and space pattern and In both cases of the hole and space pattern, the ID bias is excellent, the process margin relating to the depth of focus (DOF) is excellent, the pattern shape is excellent with high sensitivity, and the resolution, dry etching resistance, and developability are also excellent. Do.

In addition, the radiation sensitive resin composition of this invention which contains polysiloxane (1-1) which has two types of acid dissociable groups different from acid dissociation property as a resin component is a case of both a line and space pattern and a hole and space pattern. All of them have excellent process margins, particularly with regard to depth of focus (DOF), high sensitivity, and also excellent resolution, dry etching resistance, developability, and the like.

Moreover, the radiation sensitive resin composition of this invention containing polysiloxane (1) and polysiloxane (1-1) can ensure the favorable balance of the said outstanding characteristic.

Therefore, the radiation sensitive resin composition of this invention can be used suitably as a chemically amplified resist for microfabrication which uses various radiations, such as far ultraviolet rays, an electron beam, and X-rays.

Claims (19)

The silane compound represented by following formula (I). <Formula I>

In formula (I), each R independently of each other represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and R ¹ and R ² are each independently a fluorine atom, a straight or branched carbon group of 1 to 4 carbon atoms. An alkyl group or a C1-C4 linear or branched fluorinated alkyl group is represented, n is 0 or 1, k is 1 or 2, i is an integer of 0-8 when k = 1, k = 2 days Is an integer of 0 to 10. The silane compound according to claim 1, wherein in formula (I), each R is independently of one another a methyl group or an ethyl group. The silane compound of claim 1, wherein in formula (I), R ¹ is a methyl group or an ethyl group and i is 0. 3. The silane compound of claim 1, wherein n is zero in formula (I). A polysiloxane having a polystyrene reduced weight average molecular weight of 500 to 1,000,000 by gel permeation chromatography (GPC) having a structural unit represented by the following formula (1). <Formula 1>

In formula (1), R ¹ and R ² independently of each other represent a fluorine atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched fluorinated alkyl group having 1 to 4 carbon atoms, and n is 0 or 1 K is 1 or 2, i is an integer of 0-8 when k = 1, and an integer of 0-10 when k = 2. A polysiloxane having a polystyrene reduced weight average molecular weight of 500 to 1,000,000 by gel permeation chromatography (GPC) having a structural unit represented by the following formula (1) and a structural unit represented by the following formula (3). <Formula 1>

<Formula 3>

In formula (1), R ¹ and each R ² independently of each other represent a fluorine atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched fluorinated alkyl group having 1 to 4 carbon atoms, and n is 0 or 1, k is 1 or 2, i is an integer of 0 to 8 when k = 1, an integer of 0 to 10 when k = 2, In the general formula (3), E represents a monovalent organic group having a fluorinated hydrocarbon group. Polystyrene reduced weight average molecular weight by gel permeation chromatography (GPC) having a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2) except for the structural unit represented by the formula (1) Polysiloxanes from 500 to 1,000,000. <Formula 1>

<Formula 2>

In formula (1), R ¹ and each R ² independently of each other represent a fluorine atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched fluorinated alkyl group having 1 to 4 carbon atoms, and n is 0 or 1, k is 1 or 2, i is an integer of 0 to 8 when k = 1, an integer of 0 to 10 when k = 2, In formula (2), each R ³ independently of each other represents 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 derivative thereof, or any two R ^{3 s} mutually To form a C4-C20 divalent alicyclic hydrocarbon group or a derivative thereof together with the carbon atoms to which each is bonded, and the remaining R ³ is a linear or branched alkyl group having 1 to 4 carbon atoms or 4 to 4 carbon atoms. 20 monovalent alicyclic hydrocarbon group or its derivative is shown, m is 0 or 1. 8. The polysiloxane according to claim 7, wherein in formula (2), each R ³ is independently a linear or branched alkyl group having 1 to 4 carbon atoms. Gel permeation chromatography (GPC) having a structural unit represented by the following formula (1), a structural unit represented by the following formula (2) except for the structural unit represented by the formula (1), and a structural unit represented by the following formula (3) The polysiloxane of the weight average molecular weight in terms of polystyrene by () is 500-1,000,000. <Formula 1>

<Formula 2>

<Formula 3>

In formula (1), R ¹ and each R ² independently of each other represent a fluorine atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched fluorinated alkyl group having 1 to 4 carbon atoms, and n is 0 or 1, k is 1 or 2, i is an integer of 0 to 8 when k = 1, an integer of 0 to 10 when k = 2, In formula (2), each R ³ independently represents a linear or branched alkyl group having 1 to 4 carbon atoms, a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms, or a derivative thereof, or any two R ^{3 s} mutually To form a C4-C20 divalent alicyclic hydrocarbon group or a derivative thereof together with the carbon atoms to which each is bonded, and the remaining R ³ is a linear or branched alkyl group having 1 to 4 carbon atoms or 4 to 4 carbon atoms. 20 monovalent alicyclic hydrocarbon group or a derivative thereof, m is 0 or 1, In the general formula (3), E represents a monovalent organic group having a fluorinated hydrocarbon group. The radiation sensitive resin composition containing (A) polysiloxane of Claim 5, and (B) radiation sensitive acid generator. The radiation sensitive resin composition containing (A) polysiloxane of Claim 6, and (B) radiation sensitive acid generator. The radiation sensitive resin composition containing (A) polysiloxane of Claim 7 and (B) radiation sensitive acid generator. A radiation sensitive resin composition comprising (A) the polysiloxane of claim 8 and (B) a radiation sensitive acid generator. The radiation sensitive resin composition containing (A) polysiloxane of Claim 9, and (B) radiation sensitive acid generator. The radiation sensitive resin composition of Claim 10 whose (B) radiation sensitive acid generator is a compound which produces sulfonic acid by exposure. The radiation sensitive resin composition of Claim 11 whose (B) radiation sensitive acid generator is a compound which produces sulfonic acid by exposure. The radiation sensitive resin composition of Claim 12 whose (B) radiation sensitive acid generator is a compound which produces sulfonic acid by exposure. The radiation sensitive resin composition according to claim 13, wherein the radiation sensitive acid generator (B) is a compound which generates sulfonic acid by exposure. The radiation sensitive resin composition of Claim 14 whose (B) radiation sensitive acid generator is a compound which produces sulfonic acid by exposure.