JP2013152375A - Negative radiation-sensitive composition, pattern forming method and method for manufacturing insulating film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a negative radiation-sensitive composition capable of forming a fine resist pattern and satisfying lithographic properties such as LWR.SOLUTION: There is provided a negative radiation-sensitive composition which comprises [A] a polysiloxane, [B] a radiation-sensitive acid generator, [C] a radiation-sensitive base generator and [D] a solvent. Further, the ratio of the equivalent of [B] the acid generator to the equivalent of [C] the base generator is preferably 0.1 or more and 100 or less, and [B] the acid generator is an onium salt compound and [C] the base generator is a nitrogen-containing compound.

Description

  The present invention relates to a negative radiation sensitive composition, a pattern forming method using the same, and a method for producing an insulating film.

  In the microfabrication field for manufacturing integrated circuit elements and the like, lithography technology using short-wavelength radiation represented by KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), etc. in order to obtain a higher degree of integration Development is underway.

  As a lithography material for such short-wavelength radiation, a chemically amplified resist containing a component having an acid-dissociable group and a radiation-sensitive acid generator that generates an acid upon irradiation with radiation is generally used. It has been.

  On the other hand, in the fine processing field, it is desired to form a finer resist pattern, and for example, an immersion exposure method is known as the forming method. According to this immersion exposure method, lenses and exposure light sources mounted on existing equipment can be used, which is superior in terms of cost, and resolution equivalent to that obtained when the light source wavelength of the exposure equipment is shortened. Etc. are obtained. Various negative radiation-sensitive compositions used for such immersion exposure methods have been developed (see Patent Documents 1 to 3).

  However, in recent years when further miniaturization of devices is progressing, further miniaturization of a resist pattern is desired. Further, such fine resist pattern has excellent Line Width Lowness (LWR). Lithographic properties such as are desired.

International Publication No. 2004/068242 JP 2005-173474 A JP 2006-48029 A

  The present invention has been made based on the above circumstances, and an object of the present invention is to provide a negative radiation-sensitive composition that can form a fine resist pattern and satisfies lithography characteristics such as LWR. .

The invention made to solve the above problems is
[A] polysiloxane,
[B] Radiation-sensitive acid generator (hereinafter sometimes referred to as “[B] acid generator”),
[C] A negative radiation-sensitive composition containing a radiation-sensitive base generator (hereinafter sometimes referred to as “[C] base generator”), and [D] a solvent.

  In the negative radiation sensitive composition of the present invention, the [B] acid generator and the [C] base generator coexist in the composition. Therefore, in the exposure process, which is one process of forming a resist pattern, an acid is generated by the light that has passed through the mask, and in addition, a base is simultaneously generated according to the light intensity distribution. For example, when forming a line pattern, a base capable of neutralizing the acid is generated with respect to the acid generated in the exposed area where the light intensity is strong, in other words, in the vicinity of the center line of the line-shaped exposed area. Thus, the same behavior as that of the unexposed portion is exhibited. That is, the amount of acid in the film in the exposed area where the light intensity is high becomes a very small amount, and the crosslinking of [A] polysiloxane hardly proceeds and becomes soluble in the developer as in the unexposed area. On the other hand, in the exposed portion having a medium light intensity, in other words, in the portion other than the vicinity of the center line of the linear exposed portion, the generated amount of base is such that the acid cannot be neutralized with respect to the generated acid. As a result, the acid remains in the film, and the crosslinking of [A] polysiloxane proceeds and becomes hardly soluble in the developer. Therefore, according to the negative radiation sensitive composition, a fine pattern divided into two can be formed with the vicinity of the center line as a boundary in one line-shaped exposed portion. Further, such a pattern is excellent in lithography characteristics such as LWR.

  [B] The ratio of the equivalent of the [C] base generator to the equivalent of the acid generator is preferably 0.1 or more and 100 or less. In this way, by setting the generation amount of acid and base to a specific ratio, it is possible to control the neutralization reaction in the above-exposed exposed portion having a high light intensity and the exposed portion having a medium light intensity, and more clearly. A fine pattern divided into two can be formed. Here, “equivalent” means a value obtained by dividing the number of moles by the valence (the number of acids or bases that can be generated from one molecule).

  [B] The acid generator is preferably an onium salt compound, and the [C] base generator is preferably a nitrogen-containing compound. By using [B] acid generator and [C] base generator as the above specific compound, when the pattern formed is, for example, a line-and-space pattern, one line is more clearly divided into two. A divided fine pattern can be formed.

（式（１）中、ａは、０〜３の整数である。Ｒ^１は、１価の有機基である。但し、Ｒ^１が複数存在する場合、複数のＲ^１は、同一又は異なってもよい。Ｘ^１は、塩素原子、臭素原子又はＯＲ^２である。Ｒ^２は、１価の有機基である。但し、Ｘ^１が複数存在する場合、複数のＸ^１は、同一又は異なってもよい。） [A] The polysiloxane preferably has a structural unit derived from a hydrolyzable silane compound represented by the following formula (1).

(In the formula (1), a is .R ¹ is an integer of 0 to 3 is a monovalent organic group. However, ^{if R 1} there are a plurality, the plurality of ^{R 1} may be the same or different and which may .X ¹ is chlorine atom, a bromine atom or oR ² .R ² is a monovalent organic group. However, when ^{the X 1} there are a plurality, the plurality of ^{X 1} are the same or different May be good.)

  [A] Since the polysiloxane has a structural unit derived from the hydrolyzable silane compound represented by the above formula (1), the [A] polysiloxane can be more efficiently used in an exposed portion having a medium light intensity. Crosslinking can proceed. Moreover, since the negative radiation sensitive composition [A] polysiloxane partially contains Si-C units, it forms an insulating film having high strength, low water absorption, and excellent stability and durability. can do.

  The negative radiation sensitive composition preferably further contains an [E] acid diffusion inhibitor. When the negative radiation sensitive composition further contains an [E] acid diffusion inhibitor, the diffusion phenomenon of the acid generated from the [B] acid generator upon exposure in the resist film is controlled, and a desired neutralization reaction is achieved. Can be achieved.

  The negative radiation-sensitive composition preferably further contains a polymer having [F] fluorine atoms (hereinafter sometimes referred to as “[F] polymer”). When the negative radiation sensitive composition contains the [F] polymer, the hydrophobicity of the resist film is improved, and even when immersion exposure is performed, the material elution is excellent, and the negative radiation sensitive composition. Usefulness for immersion exposure of objects increases.

（式（３）中、Ｒ^１２は、水素原子、フッ素原子、メチル基又はトリフルオロメチル基である。Ｒ^１３は、フッ素原子を有する炭素数１〜６の直鎖状若しくは分岐状のアルキル基、又はフッ素原子を有する炭素数４〜２０の１価の脂環式炭化水素基である。但し、上記アルキル基及び脂環式炭化水素基は、水素原子の一部又は全部が置換されていてもよい。）

（式（４）中、Ｒ^１４は、水素原子、フッ素原子、メチル基又はトリフルオロメチル基である。Ｒ^１５は、（ｋ＋１）価の連結基である。Ｘ^３は、フッ素原子を有する２価の連結基である。Ｒ^１６は、水素原子又は１価の有機基である。ｋは、１〜３の整数である。但し、Ｘ^３及びＲ^１６が複数存在する場合、複数のＸ^３及びＲ^１６は、同一又は異なってもよい。）

（式（５）中、Ｒ^１７は、フッ素原子を有する炭素数１〜６の直鎖状若しくは分岐状のアルキル基、又はフッ素原子を有する炭素数４〜２０の１価の脂環式炭化水素基である。但し、上記アルキル基及び脂環式炭化水素基は、水素原子の一部又は全部が置換されていてもよい。ｃは、０〜２の整数である。ｄは、０〜４の整数である。） [F] The polymer preferably has at least one structural unit selected from the group consisting of a plurality of structural units represented by the following formulas (3), (4) and (6).

(In Formula (3), R ¹² is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. R ¹³ is a C 1-6 linear or branched alkyl group having a fluorine atom. Or a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms having a fluorine atom, provided that the alkyl group and the alicyclic hydrocarbon group are partially or entirely substituted with hydrogen atoms. May be good.)

(In formula (4), R ¹⁴ is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group. R ¹⁵ is a (k + 1) -valent linking group. X ³ is a fluorine atom having 2 atoms. is a valence connecting group ^{.R 16} is .k a hydrogen atom or a monovalent organic group is an integer of 1 to 3. However, ^{if X 3} and ^{R 16} there are a plurality, a plurality of ^{X 3} And R ¹⁶ may be the same or different.)

(In the formula (5), R ¹⁷ is a linear or branched alkyl group having 1 to 6 carbon atoms having a fluorine atom, or a monovalent alicyclic hydrocarbon having 4 to 20 carbon atoms having a fluorine atom. Provided that the alkyl group and the alicyclic hydrocarbon group may be partially or entirely substituted with hydrogen atoms, c is an integer of 0 to 2, and d is 0 to 4; Is an integer.)

  The [F] polymer has the specific structural unit described above, so that it is more excellent in suppressing substance elution, and as a result, the usefulness of the negative radiation-sensitive composition for immersion exposure can be further enhanced.

The pattern forming method of the present invention comprises:
(1) Using the negative radiation sensitive composition, a step of forming a coating film on a substrate,
(2) a step of exposing the coating film,
(3) a step of heating the exposed coating film, and (4) a step of developing the heated coating film with a developer.

  According to the formation method, a negative radiation-sensitive composition that can form a fine resist pattern and satisfies lithography characteristics such as LWR can be provided.

The manufacturing method of the insulating film of the present invention is as follows:
(1) Using the negative radiation sensitive composition, a step of forming a coating film on a substrate,
(2) a step of exposing the coating film,
(3) a step of heating the exposed coating film;
(4) The process which develops the said heated coating film with a developing solution, (5) The process of performing a hardening process by high energy ray irradiation and / or a heating is included.

  The insulating film formed by the manufacturing method is also suitable as a patterned wiring insulator that requires extremely fine patterning performance, an inorganic sacrificial film for processing semiconductor materials, or the like.

  The “radiation” of the “negative radiation-sensitive composition” in the present specification is a concept including visible light, ultraviolet light, far ultraviolet light, X-rays, charged particle beams and the like.

  The present invention can provide a negative radiation-sensitive composition capable of forming a fine resist pattern and satisfying lithography properties such as LWR, and a pattern forming method using such a composition. Further, the cured product of the obtained pattern is suitable as an insulating film such as a patterned wiring insulator or an inorganic sacrificial film for processing a semiconductor material that requires extremely fine patterning performance.

<Negative type radiation sensitive composition>
The negative radiation sensitive composition of the present invention contains [A] polysiloxane, [B] acid generator, [C] base generator, and [D] solvent. According to the negative radiation-sensitive composition, for example, when a line-and-space pattern is formed, as a result, a fine pattern divided into two with a central line vicinity as a boundary in one line-shaped exposed portion Can be formed. Further, such a pattern is excellent in lithography characteristics such as LWR. The said negative radiation sensitive composition can contain an [E] acid diffusion inhibitor, a [F] polymer, and another arbitrary component as needed. Hereinafter, each component will be described in detail.

<[A] polysiloxane>
[A] The polysiloxane is not particularly limited as long as it is a polymer of a compound having a siloxane bond. [A] The polysiloxane can be usually obtained by hydrolytic condensation of a hydrolyzable silane compound in the presence of a catalyst.

  As the hydrolyzable silane compound, those having a structural unit derived from the water-decomposable silane compound represented by the formula (1) are preferable. [A] Since the polysiloxane has a structural unit derived from the hydrolyzable silane compound represented by the above formula (1), the [A] polysiloxane can be more efficiently used in an exposed portion having a medium light intensity. Crosslinking can proceed.

In formula (1), a is an integer of 0-3. R ¹ is a monovalent organic group. However, if the R ¹ there are a plurality, the plurality of R ¹ may be the same or different. X ¹ is a chlorine atom, a bromine atom or OR ² . R ² is a monovalent organic group. However, if the X ¹ there are a plurality, the plurality of X ¹ may be the same or different.

Examples of the monovalent organic group represented by R ¹ include a fluorine atom, an alkylcarbonyloxy group, and a linear or branched alkyl group having 1 to 20 carbon atoms.

Examples of the alkylcarbonyloxy group represented by R ¹ include a methylcarbonyloxy group, an ethylcarbonyloxy group, a propylcarbonyloxy group, and a butylcarbonyloxy group.

Examples of the linear or branched alkyl group having 1 to 20 carbon atoms represented by R ¹ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group.

Examples of the monovalent organic group represented by R ¹ include organic groups having one or more carbon-oxygen single bonds or carbon-oxygen double bonds. Such an organic group is a group containing an epoxy group, an ester group, an alkoxy group, a hydroxy group, and the like, and examples thereof include an organic group represented by the following formula. In the following formula, (Si) represents a bonding site with Si.

  In addition, examples of the organic group include organic groups containing a silicon-silicon bond, and are represented by the following formula, for example.

Examples of the monovalent organic group represented by R ² include a monovalent linear hydrocarbon group having 1 to 30 carbon atoms, a monovalent aliphatic cyclic hydrocarbon group having 3 to 30 carbon atoms, and 6 to 30 carbon atoms. And hydrocarbon groups such as monovalent aromatic hydrocarbon groups, and groups in which some or all of the hydrogen atoms of these groups are substituted with substituents such as epoxy groups, alkoxy groups and hydroxy groups. .

  Examples of the monovalent linear hydrocarbon group having 1 to 30 carbon atoms include alkyl groups having 1 to 30 carbon atoms such as a methyl group, an ethyl group, a propyl group, and a butyl group; an ethenyl group, a propenyl group, and a butenyl group. And alkynyl groups having 1 to 30 carbon atoms such as alkynyl groups having 1 to 30 carbon atoms such as ethynyl group, propynyl group and butynyl group.

  Examples of the monovalent aliphatic cyclic hydrocarbon group having 3 to 30 carbon atoms include monocyclic saturated hydrocarbon groups such as cyclobutyl group and cyclohexyl group; and polycyclic unsaturated hydrocarbon groups such as cyclobutenyl group and cyclohexenyl group. A polycyclic saturated hydrocarbon group such as a bicyclo [2.2.1] heptanyl group; a polycyclic unsaturated hydrocarbon group such as a bicyclo [2.2.1] heptenyl group;

  Examples of the monovalent aromatic hydrocarbon group having 6 to 30 carbon atoms include a phenyl group, a biphenyl group, a terphenyl group, a benzyl group, and a naphthyl group.

  Preferable examples of the hydrolyzable silane compound represented by the above formula (1) include silane compounds such as tetraalkoxysilane, trialkoxysilane, dialkoxysilane.

  Examples of the tetraalkoxysilane include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, and tetra-iso-propoxysilane. Of these, tetramethoxysilane and tetraethoxysilane are preferred.

  Examples of trialkoxysilane include 3- (trimethoxysilyl) propyl methacrylate, 3- (triethoxysilyl) propyl methacrylate, N-3- (methacryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, 2- (Trimethoxysilyl) ethyl methacrylate, 2- (triethoxysilyl) ethyl methacrylate, trimethoxysilylmethyl methacrylate, methacryloxypropyltris (methoxyethoxy) silane, triethoxysilylmethyl methacrylate, 3- [tris (trimethylsiloxy) silyl] Propyl methacrylate, 3- [tris (dimethylvinylsiloxy)] propyl methacrylate, 3- (trimethoxysilyl) propyl acrylate, 3- (triethoxysilyl) pro Acrylate, 2-cyanoethyltrimethoxysilane, 2-cyanoethyltriethoxysilane, 2-cyanoethyltri-n-propoxysilane, 2-cyanoethyltri-iso-propoxysilane, trimethoxysilane, triethoxysilane, tri-n-propoxy Silane, tri-iso-propoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-iso-propoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-n-propoxysilane, Ethyltri-iso-propoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri-n-propoxysilane, vinyltri-iso-propoxysilane, n-propyl Limethoxysilane, n-propyltriethoxysilane, n-propyltri-n-propoxysilane, n-propyltri-iso-propoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane, i-propyltri- n-propoxysilane, i-propyltri-iso-propoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-butyltri-n-propoxysilane, n-butyltri-iso-propoxysilane, sec-butyl Trimethoxysilane, sec-butyl-i-triethoxysilane, sec-butyl-tri-n-propoxysilane, sec-butyl-tri-iso-propoxysilane, t-butyltrimethoxysilane, t-butyltriethoxysilane, t-butyltri-n -Propoxysilane, t-butyltri-iso-propoxysilane, cyclopropyltrimethoxysilane, cyclopropyltriethoxysilane, cyclopropyl-tri-n-propoxysilane, cyclopropyl-tri-iso-propoxysilane, cyclobutyltrimethoxysilane , Cyclobutyltriethoxysilane, cyclobutyl-tri-n-propoxysilane, cyclobutyl-tri-iso-propoxysilane, cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, cyclopentyl-tri-n-propoxysilane, cyclopentyl-tri-iso- Propoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, cyclohexyl-tri-n-propoxysilane, cyclohexyl-tri iso-propoxysilane, cyclohexenyltrimethoxysilane, cyclohexenyltriethoxysilane, cyclohexenyl-tri-n-propoxysilane, cyclohexenyl-tri-iso-propoxysilane, cyclohexenylethyltrimethoxysilane, cyclohexenylethyltriethoxysilane , Cyclohexenylethyl-tri-n-propoxysilane, cyclohexenylethyltri-iso-propoxysilane, cyclooctanyltrimethoxysilane, cyclooctanyltriethoxysilane, cyclooctanyl-tri-n-propoxysilane, cyclooctanyl -Tri-iso-propoxysilane, cyclopentadienylpropyltrimethoxysilane, cyclopentadienylpropyltriethoxysilane, cyclopentadiene Rupropyl-tri-n-propoxysilane, cyclopentadienylpropyl-tri-iso-propoxysilane, bicycloheptenyltrimethoxysilane, bicycloheptenyltriethoxysilane, bicycloheptenyl-tri-n-propoxysilane, bicycloheptenyl -Tri-iso-propoxysilane, bicycloheptyltrimethoxysilane, bicycloheptyltriethoxysilane, bicycloheptyl-tri-n-propoxysilane, bicycloheptyl-tri-iso-propoxysilane, adamantyltrimethoxysilane, adamantyltriethoxysilane, And adamantyl-tri-n-propoxysilane, adamantyl-tri-iso-propoxysilane, and the like. Further, as a light-absorbing monomer, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltri-n-propoxysilane, phenyltri-iso-propoxysilane, benzyltrimethoxysilane, benzyltriethoxysilane, benzyltri-n-propoxysilane Benzyltri-iso-propoxysilane, tolyltrimethoxysilane, tolyltriethoxysilane, tolyltri-n-propoxysilane, tolyltri-iso-propoxysilane, phenethyltrimethoxysilane, phenethyltriethoxysilane, phenethyltri-n-propoxysilane, Phenethyl tri-iso-propoxy silane, naphthyl trimethoxy silane, naphthyl triethoxy silane, naphthyl tri-n-propoxy silane, naphthyl tri-i o- propoxysilane, and the like.

  Among these trialkoxysilanes, 2-cyanoethyltrimethoxysilane, 3- (trimethoxysilyl) propyl methacrylate, 3- (triethoxysilyl) propyl methacrylate, trimethoxysilylmethyl methacrylate, 2- (trimethoxysilyl) ethyl methacrylate 2- (triethoxysilyl) ethyl methacrylate, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, n-propyltrimethoxysilane, n- Propyltriethoxysilane, iso-propyltrimethoxysilane, iso-propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, iso Butyltrimethoxysilane, iso-butyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, cyclohexenyltrimethoxysilane, cyclohexenyl Triethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, benzyltrimethoxysilane, benzyltriethoxysilane, phenethyltrimethoxysilane, and phenethyltriethoxysilane are preferred.

  [A] The polysiloxane may contain other hydrolyzable silane compounds in addition to the above silane compounds. Although it does not specifically limit as another hydrolysable silane compound, [A] polysiloxane can further have the structural unit derived from the hydrolysable silane compound represented by following formula (2).

In said formula (2), x is an integer of 0-2. y is an integer of 0-2. z is 0 or 1. R ³ is a monovalent organic group. However, if R ³ there are a plurality, the plurality of R ³ may be the same or different. R ⁴ is a monovalent organic group. However, if the R ⁴ there are a plurality, the plurality of R ⁴ may be the same or different. R ⁵ is an oxygen atom, a sulfur atom, a phenylene group, or a group represented by — (CH ₂ ) _n —. n is an integer of 1-6. X ² is a halogen atom or OR ⁶ . R ⁶ is a monovalent organic group. However, if X ² there are a plurality, the plurality of X ² may be the same or different.

Examples of the monovalent organic group represented by R ³ , R ⁴ and R ⁶ include the same groups as those described as the monovalent organic group represented by R ² described above.

Examples of the hydrolyzable silane compound represented by the above formula (2) include hexamethoxydisilane, hexaethoxydisilane, hexaphenoxydisilane, 1,1,1,2,2-pentamethoxy-2-methyldisilane, 1, 1,1,2,2-pentaethoxy-2-methyldisilane, 1,1,1,2,2-pentaphenoxy-2-methyldisilane, 1,1,1,2,2-pentamethoxy-2-ethyl Disilane, 1,1,1,2,2-pentaethoxy-2-ethyldisilane, 1,1,1,2,2-pentaphenoxy-2-ethyldisilane, 1,1,1,2,2-pentamethoxy -2-phenyldisilane, 1,1,1,2,2-pentaethoxy-2-phenyldisilane, 1,1,1,2,2-pentaphenoxy-2-phenyldisilane, 1,1,2,2- Tramethoxy-1,2-dimethyldisilane, 1,1,2,2-tetraethoxy-1,2-dimethyldisilane, 1,1,2,2-tetraphenoxy-1,2-dimethyldisilane, 1,1,2, , 2-tetramethoxy-1,2-diethyldisilane, 1,1,2,2-tetraethoxy-1,2-diethyldisilane, 1,1,2,2-tetraphenoxy-1,2-diethyldisilane, , 1,2,2-tetramethoxy-1,2-diphenyldisilane, 1,1,2,2-tetraethoxy-1,2-diphenyldisilane, 1,1,2,2-tetraphenoxy-1,2- Diphenyldisilane, 1,1,2-trimethoxy-1,2,2-trimethyldisilane, 1,1,2-triethoxy-1,2,2-trimethyldisilane, 1,1,2-triphenoxy-1, , 2-trimethyldisilane, 1,1,2-trimethoxy-1,2,2-triethyldisilane, 1,1,2-triethoxy-1,2,2-triethyldisilane, 1,1,2-triphenoxy-1 , 2,2-triethyldisilane, 1,1,2-trimethoxy-1,2,2-triphenyldisilane, 1,1,2-triethoxy-1,2,2-triphenyldisilane, 1,1,2- Triphenoxy-1,2,2-triphenyldisilane, 1,2-dimethoxy-1,1,2,2-tetramethyldisilane, 1,2-diethoxy-1,1,2,2-tetramethyldisilane, 1 , 2-diphenoxy-1,1,2,2-tetramethyldisilane, 1,2-dimethoxy-1,1,2,2-tetraethyldisilane, 1,2-diethoxy-1,1,2,2-tetraethyl Disilane, 1,2-diphenoxy-1,1,2,2-tetraethyldisilane, 1,2-dimethoxy-1,1,2,2-tetraphenyldisilane, 1,2-diethoxy-1,1,2,2 -Tetraphenyldisilane, 1,2-diphenoxy-1,1,2,2-tetraphenyldisilane, bis (trimethoxysilyl) methane, bis (triethoxysilyl) methane, bis (tri-n-propoxysilyl) methane, Bis (tri-iso-propoxysilyl) methane, bis (tri-n-butoxysilyl) methane, bis (tri-sec-butoxysilyl) methane, bis (tri-tert-butoxysilyl) methane, 1,2-bis ( Trimethoxysilyl) ethane, 1,2-bis (triethoxysilyl) ethane, 1,2-bis (tri-n-propoxysilyl) ethane 1,2-bis (tri-iso-propoxysilyl) ethane, 1,2-bis (tri-n-butoxysilyl) ethane, 1,2-bis (tri-sec-butoxysilyl) ethane, 1,2 -Bis (tri-tert-butoxysilyl) ethane, 1- (dimethoxymethylsilyl) -1- (trimethoxysilyl) methane, 1- (diethoxymethylsilyl) -1- (triethoxysilyl) methane, 1- ( Di-n-propoxymethylsilyl) -1- (tri-n-propoxysilyl) methane, 1- (di-iso-propoxymethylsilyl) -1- (tri-iso-propoxysilyl) methane, 1- (di- n-butoxymethylsilyl) -1- (tri-n-butoxysilyl) methane, 1- (di-sec-butoxymethylsilyl) -1- (tri-sec-butoxy Yl) methane, 1- (di-tert-butoxymethylsilyl) -1- (tri-tert-butoxysilyl) methane, 1- (dimethoxymethylsilyl) -2- (trimethoxysilyl) ethane, 1- (diethoxy Methylsilyl) -2- (triethoxysilyl) ethane, 1- (di-n-propoxymethylsilyl) -2- (tri-n-propoxysilyl) ethane, 1- (di-iso-propoxymethylsilyl) -2 -(Tri-iso-propoxysilyl) ethane, 1- (di-n-butoxymethylsilyl) -2- (tri-n-butoxysilyl) ethane, 1- (di-sec-butoxymethylsilyl) -2- ( Tri-sec-butoxysilyl) ethane, 1- (di-tert-butoxymethylsilyl) -2- (tri-tert-butoxysilyl) ethane;
Bis (dimethoxymethylsilyl) methane, bis (diethoxymethylsilyl) methane, bis (di-n-propoxymethylsilyl) methane, bis (di-iso-propoxymethylsilyl) methane, bis (di-n-butoxymethylsilyl) ) Methane, bis (di-sec-butoxymethylsilyl) methane, bis (di-tert-butoxymethylsilyl) methane, 1,2-bis (dimethoxymethylsilyl) ethane, 1,2-bis (diethoxymethylsilyl) Ethane, 1,2-bis (di-n-propoxymethylsilyl) ethane, 1,2-bis (di-iso-propoxymethylsilyl) ethane, 1,2-bis (di-n-butoxymethylsilyl) ethane, 1,2-bis (di-sec-butoxymethylsilyl) ethane, 1,2-bis (di-tert-butoxymethyl) Silyl) ethane, 1,2-bis (trimethoxysilyl) benzene, 1,2-bis (triethoxysilyl) benzene, 1,2-bis (tri-n-propoxysilyl) benzene, 1,2-bis (tri -Iso-propoxysilyl) benzene, 1,2-bis (tri-n-butoxysilyl) benzene, 1,2-bis (tri-sec-butoxysilyl) benzene, 1,2-bis (tri-tert-butoxysilyl) ) Benzene, 1,3-bis (trimethoxysilyl) benzene, 1,3-bis (triethoxysilyl) benzene, 1,3-bis (tri-n-propoxysilyl) benzene, 1,3-bis (tri- iso-propoxysilyl) benzene, 1,3-bis (tri-n-butoxysilyl) benzene, 1,3-bis (tri-sec-butoxysilyl) benzene Zen, 1,3-bis (tri-tert-butoxysilyl) benzene, 1,4-bis (trimethoxysilyl) benzene, 1,4-bis (triethoxysilyl) benzene, 1,4-bis (tri-n) -Propoxysilyl) benzene, 1,4-bis (tri-iso-propoxysilyl) benzene, 1,4-bis (tri-n-butoxysilyl) benzene, 1,4-bis (tri-sec-butoxysilyl) benzene 1,4-bis (tri-tert-butoxysilyl) benzene and the like.

  Of these, 1,2-bis (triethoxysilyl) ethane, 1,2-bis (trimethoxysilyl) benzene, 1,2-bis (triethoxysilyl) benzene, 1,3-bis (trimethoxysilyl) Benzene, 1,3-bis (triethoxysilyl) benzene, 1,4-bis (trimethoxysilyl) benzene, and 1,4-bis (triethoxysilyl) benzene are preferred.

  [A] Polysiloxane gel weight permeation chromatography (GPC) polystyrene-reduced weight average molecular weight (Mw) is preferably 20,000 or less, more preferably 500 or more and 18,000 or less, and 1,000 or more and 15,000 or less. Particularly preferred. [A] By making Mw of polysiloxane into the said range, the applicability | paintability of a composition and the intensity | strength and workability of the resist film obtained can be made compatible at a high level. Mw of this specification is a monodisperse using GPC columns (Tosoh Corp., 2 G2000HXL, 1 G3000HXL, 1 G4000HXL) under flow rate of 1.0 mL / min, elution solvent tetrahydrofuran, and column temperature of 40 ° C. The value measured by GPC using polystyrene as a standard.

<[A] Production method of polysiloxane>
[A] Polysiloxane is prepared by, for example, using the hydrolyzable silane compound as a starting material, dissolving the starting material in an organic solvent, and intermittently or continuously adding water to the solution to cause a hydrolytic condensation reaction. Can be manufactured. At this time, a catalyst may be used. The catalyst may be dissolved or dispersed in advance in an organic solvent, or may be dissolved or dispersed in water to be added. Moreover, as temperature for performing a hydrolysis-condensation reaction, it is 0 to 100 degreeC normally.

  In addition, when [A] polysiloxane is manufactured using a plurality of types of hydrolyzable silane compounds, a mixture of all of the plurality of types of hydrolyzable silane compounds may be subjected to a hydrolytic condensation reaction at a time, or each compound The hydrolytic condensation reaction may be carried out using a hydrolyzate or a condensate thereof, or a hydrolyzate or a condensate of a mixture of selected compounds.

  The organic solvent is not particularly limited as long as it is an organic solvent used for this kind of application. For example, methyl alcohol, ethyl alcohol, isopropyl alcohol, propylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monopropyl ether, etc. Is mentioned.

  Although it does not specifically limit as water for performing a hydrolysis-condensation reaction, It is preferable to use ion-exchange water. The amount of water used is preferably 0.25 to 3 mol, more preferably 0.3 to 2.5 mol per mol of hydrolyzable groups (alkoxy groups, etc.) of the hydrolyzable silane compound used. preferable. There is no possibility that the uniformity of the coating film formed by using water in an amount in the above range will be lowered, and there is little possibility that the storage stability of the composition will be lowered.

  Examples of the catalyst include metal chelate compounds, organic acids, inorganic acids, organic bases, inorganic bases, and the like.

  Examples of the metal chelate compound include a titanium chelate compound, a zirconium chelate compound, and an aluminum chelate compound. Specifically, compounds described in JP 2000-356854 A and the like are used.

  Examples of the organic acid include acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, sebacic acid, and gallic acid. Acid, butyric acid, meritic acid, arachidonic acid, mikimic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linolenic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzenesulfone Examples include acids, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, tartaric acid, pentafluoropropionic acid and the like.

  Examples of the inorganic acid include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid.

  Examples of the organic base include pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine, diazabicycloocrane, diazabicyclo. Nonane, diazabicycloundecene, tetramethylammonium hydroxide and the like can be mentioned.

  Examples of the inorganic base include ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide and the like.

  Of these catalysts, metal chelate compounds, organic acids and inorganic acids are preferred. The said catalyst may be used independently and may be used in combination of 2 or more type.

  As a usage-amount of a catalyst, 0.001 mass part-50 mass parts and 0.01 mass part-40 mass parts are preferable normally with respect to 100 mass parts of said hydrolysable silane compounds.

  Further, after the hydrolysis condensation reaction, it is preferable to perform a removal treatment of reaction by-products such as lower alcohols such as methanol and ethanol. By performing the removal treatment, a composition having excellent coating properties with respect to the substrate and good storage stability can be obtained.

  The method for removing the reaction by-product is not particularly limited as long as the reaction of the hydrolyzate and / or its condensate does not proceed. For example, the boiling point of the reaction by-product is higher than the boiling point of the organic solvent. If it is low, it can be distilled off under reduced pressure.

<[B] Acid generator>
[B] The acid generator is a compound that generates an acid by light that has passed through a mask in an exposure process, which is one process of forming a resist pattern. The form of the [B] acid generator contained in the negative radiation-sensitive composition may be the form of a compound as described later, the form incorporated as part of a polymer, or both of these forms.

  [B] Examples of the acid generator include onium salt compounds, sulfonimide compounds, halogen-containing compounds, diazoketone compounds, and the like. Of these [B] acid generators, onium salt compounds are preferred.

  Examples of the onium salt compounds include sulfonium salts, tetrahydrothiophenium salts, iodonium salts, phosphonium salts, diazonium salts, pyridinium salts, and the like.

  The sulfonium salt is represented by the following formula.

_R-SO ³ - ^{M +}

In the above formula, R is a monovalent organic group. M ⁺ is a cation.

Examples of the monovalent organic group represented by R include a fluorinated alkyl group and a diester group represented by (R′—OCO—CH ₂ ) ₂ —CH— *. In addition, said R ^' is respectively independently a substituted or unsubstituted C1-C30 linear or branched hydrocarbon group, a substituted or unsubstituted C3-C30 cyclic or cyclic part. It is a hydrocarbon group having a structure, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a cyclic organic group which may have a substituted or unsubstituted heteroatom having 4 to 30 carbon atoms. * It is, SO ₃ ^- shows the binding site for.

  Examples of the fluorinated alkyl group include trifluoromethyl group, nonafluoro-n-butyl group, perfluoro-n-octyl group, 2-bicyclo [2.2.1] hept-2-yl-1,1,2, 2-tetrafluoroethyl group etc. are mentioned.

  Examples of the anion having a diester group include anions represented by the following formulas.

The structure of the cation represented by M ⁺ is preferably a sulfonium cation represented by the following formula (i).

（Ｒ^ｂ１、Ｒ^ｂ２及びＲ^ｂ３は、相互に独立に、置換若しくは非置換の炭素数１〜１０の直鎖状若しくは分岐状のアルキル基、又は置換若しくは非置換の炭素数６〜１８のアリール基を示すか、或いは、Ｒ^ｂ１、Ｒ^ｂ２及びＲ^ｂ３のうちのいずれか２つが相互に結合して式中の硫黄原子と共に環状構造を形成しており、残りの１つが置換若しくは非置換の炭素数１〜１０の直鎖状若しくは分岐状のアルキル基、又は置換若しくは非置換の炭素数６〜１８のアリール基を示す。）

(R ^b1 , R ^b2 and R ^b3 are each independently a substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted aryl having 6 to 18 carbon atoms. Or any two of R ^b1 , R ^b2 and R ^b3 are bonded to each other to form a cyclic structure with a sulfur atom in the formula, and the remaining one is a substituted or unsubstituted group. A linear or branched alkyl group having 1 to 10 carbon atoms or a substituted or unsubstituted aryl group having 6 to 18 carbon atoms is shown.)

  Examples of the sulfonium cation represented by the above formula (i) include a sulfonium cation represented by the following formula.

  Examples of the sulfonium salt include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium perfluoro-n-octanesulfonate, triphenylsulfonium 2-bicyclo [2.2.1] hept- 2-yl-1,1,2,2-tetrafluoroethanesulfonate, triphenylsulfonium camphorsulfonate, 4-cyclohexylphenyldiphenylsulfonium trifluoromethanesulfonate, 4-cyclohexylphenyldiphenylsulfonium nonafluoro-n-butanesulfonate, 4-cyclohexyl Phenyldiphenylsulfonium perfluoro-n-octanesulfonate, 4-cyclohexylphenyldiphenyl Rufonium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, 4-cyclohexylphenyldiphenylsulfonium camphorsulfonate, 4-methanesulfonylphenyldiphenylsulfonium trifluoromethanesulfonate, 4-methanesulfonylphenyldiphenylsulfonium nonafluoro-n-butanesulfonate, 4-methanesulfonylphenyldiphenylsulfonium perfluoro-n-octanesulfonate, 4-methanesulfonylphenyldiphenylsulfonium 2-bicyclo [2.2.1] hept-2 -Yl-1,1,2,2-tetrafluoroethanesulfonate, 4-methanesulfonylphenyldiphenylsulfonium camphorsulfonate, triphenyl 6-phosphonium 1,1,2,2 (1-adamantanecarbonyloxy) - hexane-1-sulfonate, a compound represented by the following formula preferred.

  Examples of the tetrahydrothiophenium salt include 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate and 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium. Nonafluoro-n-butanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium perfluoro-n-octanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothio Phenium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium camphor Sulfonate, 1- (6-n-butoxynaphthalen-2-yl ) Tetrahydrothiophenium trifluoromethanesulfonate, 1- (6-n-butoxynaphthalen-2-yl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- (6-n-butoxynaphthalen-2-yl) tetrahydro Thiophenium perfluoro-n-octanesulfonate, 1- (6-n-butoxynaphthalen-2-yl) tetrahydrothiophenium 2-bicyclo [2.2.1] hept-2-yl-1,1,2 , 2-tetrafluoroethanesulfonate, 1- (6-n-butoxynaphthalen-2-yl) tetrahydrothiophenium camphorsulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium trifluoromethanesulfonate , 1- (3,5-dimethyl 4-hydroxyphenyl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium perfluoro-n-octanesulfonate, 1- (3,5- Dimethyl-4-hydroxyphenyl) tetrahydrothiophenium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, 1- (3,5-dimethyl-4 -Hydroxyphenyl) tetrahydrothiophenium camphorsulfonate and the like. Of these tetrahydrothiophenium salts, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) Tetrahydrothiophenium perfluoro-n-octane sulfonate and 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium nonafluoro-n-butane sulfonate are preferred.

  Examples of the iodonium salt include diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium perfluoro-n-octanesulfonate, diphenyliodonium 2-bicyclo [2.2.1] hept-2-yl. -1,1,2,2-tetrafluoroethanesulfonate, diphenyliodonium camphorsulfonate, bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium nonafluoro-n-butanesulfonate Bis (4-t-butylphenyl) iodonium perfluoro-n-octanesulfonate, bis (4-t-butylphenyl) iodonium 2-bicyclo [2 2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, bis (4-t- butylphenyl) iodonium camphorsulfonate, and the like. Of these iodonium salts, bis (4-t-butylphenyl) iodonium nonafluoro-n-butanesulfonate is preferred.

Examples of the sulfonimide compound include N- (trifluoromethanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (nonafluoro-n-butanesulfonyloxy) bicyclo. [2.2.1] Hept-5-ene-2,3-dicarboximide, N- (perfluoro-n-octanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3 -Dicarboximide, N- (2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonyloxy) bicyclo [2.2.1] hept-5 ene-2,3-dicarboximide, N- (2- (3- tetracyclo ^[4.4.0.1 2,5 ^{.1 7,10]} dodecanyl) -1,1-difluoroethanesulfonate Nyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (camphorsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-di Carboximide etc. can be mentioned. Of these sulfonimide compounds, N- (trifluoromethanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide is preferred.

  Of these, sulfonium salts are preferred from the viewpoint of control of sensitivity, acidity, and diffusibility.

  These [B] acid generators may be used alone or in combination of two or more. [B] The amount used when the acid generator is “agent” is preferably 0.01 parts by mass or more and 25 parts by mass or less, and 0.1 parts by mass or more with respect to 100 parts by mass of [A] polysiloxane. 20 mass parts or less are more preferable. [B] When the amount of the acid generator used is less than 0.01 parts by mass, the amount of acid generated becomes too small, and the effects of the present invention may not be exhibited at all. On the other hand, if the amount exceeds 25 parts by mass, the amount of acid generated becomes too large, and the desired neutralization reaction may not be achieved.

<[C] Base generator>
[C] The base generator is a compound that generates a base in accordance with the intensity distribution of the light that has passed through the mask in the exposure step, which is one step of forming a resist pattern simultaneously with the above [B] acid generator. The form of the [C] base generator contained in the negative radiation-sensitive composition may be a compound form as described later, a form incorporated as part of a polymer, or both forms.

  [C] The base generator is preferably a nitrogen-containing compound.

Examples of the nitrogen-containing compound include 2-hydroxy-2-phenylacetophenone N-cyclohexyl carbamate, o-nitrobenzyl N-cyclohexyl carbamate, 3,5-dimethoxybenzyl N-cyclohexyl carbamate, dibenzoin isophorone dicarbamate, 2-nitro. Benzylcyclohexyl carbamate, o-nitrobenzyl-N, N-diisopropylcarbamate, 1- (2-nitrophenyl) ethylcyclohexyl carbamate, 2,6-dinitrobenzyl cyclohexyl carbamate, 1- (2,6-dinitrophenyl) ethyl cyclohexyl carbamate 1- (3,5-dimethoxyphenyl) -1-methylethyl cyclohexyl carbamate, 1-benzoyl-1-phenylmethyl cyclohexyl car Carbamates such as bamate, 2-benzoyl-2-hydroxy-2-phenylethyl cyclohexyl carbamate, 1,2,3-benzenetriyl tris (cyclohexyl carbamate);
N-cyclohexyl-2-naphthalenesulfonamide, N-cyclohexyl p-toluenesulfonamide, α- (cyclohexylcarbamoyloxyimino) -α- (4-methoxyphenyl) acetonitrile, N- (cyclohexylcarbamoyloxy) succinimide, etc. Amides;
[[(2-nitrobenzyl) oxy] carbonyl] cyclohexylamine, N-[[(2-nitrophenyl) -1-methylmethoxy] carbonyl] cyclohexylamine, N-[[(2,6-dinitrophenyl) -1 -Methylmethoxy] carbonyl] cyclohexylamine, N-[[(2-nitrophenyl) -1- (2′-nitrophenyl) methoxy] carbonyl] cyclohexylamine, N-[[(2,6-dinitrophenyl) -1 Amines such as-(2 ', 6'-dinitrophenyl) methoxy] carbonyl] cyclohexylamine;
Examples thereof include compounds represented by the following formulas (c-1) to (c-26).

（式（ｃ−１）及び（ｃ−３）中、Ｒ^ｃ１〜Ｒ^ｃ６は、それぞれ独立してメチル基、フェニル基又はナフチル基である。）

(In formulas (c-1) and (c-3), R ^{c1 to} R ^c6 are each independently a methyl group, a phenyl group, or a naphthyl group.)

（式（ｃ−５）中、Ｒ^ｃ７〜Ｒ^ｃ９は、それぞれ独立してメチル基又はエチル基である。）

(In formula (c-5), R ^{c7 to} R ^c9 are each independently a methyl group or an ethyl group.)

（式（ｃ−９）中、Ｒ^ｃ１０〜Ｒ^ｃ１２は、それぞれ独立してフェニル基、３，５−ジメトキシフェニル基、４−メトキシフェニル基、ナフチル基、又は４−チオメチルフェニル基である。）

(In formula (c-9), R ^{c10 to} R ^c12 each independently represent a phenyl group, a 3,5-dimethoxyphenyl group, a 4-methoxyphenyl group, a naphthyl group, or a 4-thiomethylphenyl group. )

（式（ｃ−１５）中、Ｒ^ｃ１３及びＲ^ｃ１４は、それぞれ独立して水素原子、２−ニトロフェニル基、又は２，６−ジニトロフェニル基である。但し、Ｒ^ｃ１３とＲ^ｃ１４がいずれも水素原子である場合はない。また、上記式（ｃ−１６）中、Ｒ^ｃ１５は、２−ニトロフェニル基、２，６−ジニトロフェニル基又は２，４−ジニトロフェニル基である。Ｒ^ｃ１６は、水素原子又はメチル基である。上記式（ｃ−１７）及び（ｃ−１８）中、Ｒ^ｃ１７〜Ｒ^ｃ２０は、それぞれ独立して２−ニトロフェニル基又は２，６−ジニトロフェニル基である。）

(In formula (c-15), R ^c13 and R ^c14 each independently represent a hydrogen atom, a 2-nitrophenyl group, or a 2,6-dinitrophenyl group, provided that both R ^c13 and R ^c14 are In the formula (c-16), R ^c15 represents a 2-nitrophenyl group, a 2,6-dinitrophenyl group, or a 2,4-dinitrophenyl group, and R ^c16 represents a hydrogen atom. a hydrogen atom or a methyl group. in the formula (c17) and ^{(c-18), R c17} ~R c20 are each independently a 2-nitrophenyl group or a 2,6-dinitrophenyl group .)

  These [C] base generators may be used alone or in combination of two or more. [C] The amount used when the base generator is an “agent” is preferably 0.1 part by mass or more and 20 parts by mass or less, with respect to 100 parts by mass of [A] polysiloxane, and 1 part by mass or more and 15 parts by mass. Part or less is more preferable. [C] When the amount of the base generator used is less than 0.1 parts by mass, a base sufficient to neutralize the acid generation amount may not be generated in the exposed area where the light intensity is high. On the other hand, when the amount exceeds 25 parts by mass, the amount of generated base is excessively large in the exposed portion having a medium light intensity, that is, the amount of acid generated is excessively small, and as a result, there is a possibility that a resist pattern cannot be formed. .

  [B] The ratio of the equivalent of the [C] base generator to the equivalent of the acid generator is preferably 0.1 or more and 100 or less. In this way, by setting the generation amount of acid and base to a specific ratio, it is possible to control the neutralization reaction in the above-exposed exposed portion having a high light intensity and the exposed portion having a medium light intensity, and more clearly. A fine pattern divided into two can be formed.

  [B] The acid generator is preferably an onium salt compound, and the [C] base generator is preferably a nitrogen-containing compound. By using [B] acid generator and [C] base generator as the specific compound, it is possible to form a fine pattern more clearly divided into two. In this case, the blending amount of the [C] base generator with respect to the blending amount of the [B] acid generator is preferably 0.1 to 200 parts by weight, more preferably 0.2 to 150 parts by weight. .

<[D] solvent>
The negative radiation sensitive composition usually contains a [D] solvent. [D] Examples of the solvent include alcohol solvents, ketone solvents, amide solvents, ether solvents, ester solvents, and mixed solvents thereof.

Examples of alcohol solvents include methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, sec-butanol, tert-butanol, n-pentanol, iso-pentanol, 2-methylbutanol, sec-pentanol, tert-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, 3-heptanol, n-octanol, 2-ethylhexanol , Sec-octanol, n-nonyl alcohol, 2,6-dimethyl-4-heptanol, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec -Monoalcohol solvents such as heptadecyl alcohol, furfuryl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, diacetone alcohol;
Ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, 2 -Polyhydric alcohol solvents such as ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol;
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl Ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol Monomethyl ether, dipropylene glycol monoethyl ether, polyhydric alcohol partial ether solvents such as dipropylene glycol monopropyl ether.

  Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-iso-butyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone, methyl-n- Ketones such as hexyl ketone, di-iso-butyl ketone, trimethylnonanone, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, diacetone alcohol, acetophenone A solvent is mentioned.

  Examples of the amide solvents include N, N′-dimethylimidazolidinone, N-methylformamide, N, N-dimethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpropionamide, N-methylpyrrolidone and the like can be mentioned.

  Examples of the ester solvents include diethyl carbonate, propylene carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, iso-propyl acetate, n-butyl acetate, iso-butyl acetate, sec sec -Butyl, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methyl pentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methyl cyclohexyl acetate, n-nonyl acetate, acetoacetic acid Methyl, ethyl acetoacetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol acetate Cole mono-n-butyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, diacetic acid Glycol, methoxytriglycol acetate, ethyl propionate, n-butyl propionate, iso-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate , Diethyl malonate, dimethyl phthalate, diethyl phthalate and the like.

Examples of other solvents include n-pentane, iso-pentane, n-hexane, iso-hexane, n-heptane, iso-heptane, 2,2,4-trimethylpentane, n-octane, iso-octane, cyclohexane, Aliphatic hydrocarbon solvents such as methylcyclohexane;
Fragrances such as benzene, toluene, xylene, mesitylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, iso-propylbenzene, diethylbenzene, iso-butylbenzene, triethylbenzene, di-iso-propylbenzene and n-amylnaphthalene Group hydrocarbon solvents;
And halogen-containing solvents such as dichloromethane, chloroform, chlorofluorocarbon, chlorobenzene, and dichlorobenzene.

  Of these solvents, propylene glycol monomethyl ether acetate and cyclohexanone are preferred. In addition, these [D] solvents may be used independently and may use 2 or more types together.

<[E] Acid diffusion inhibitor>
The negative radiation sensitive composition may further contain an [E] acid diffusion inhibitor. When the negative radiation-sensitive composition further contains an [E] acid diffusion inhibitor, the diffusion phenomenon of the acid generated from the [B] acid generator upon exposure in the resist film can be controlled by a neutralization reaction. And variation in pattern size can be further reduced. The content of the [E] acid diffusion inhibitor in the negative radiation-sensitive composition is a polymer in a free compound form (hereinafter sometimes referred to as “[E] acid diffusion inhibitor” as appropriate). May be incorporated as a part of or both of these forms.

  [E] Examples of the acid diffusion inhibitor include compounds represented by the following formulas.

In said formula, R < ⁷ > -R < ¹¹ > is respectively independently a hydrogen atom or a linear, branched, cyclic C1-C20 alkyl group, an aryl group, or an aralkyl group. However, these groups may have a substituent. In addition, R ⁷ and R ⁸ are bonded to each other with a nitrogen atom to which each is bonded and / or R ⁹ and R ¹⁰ are bonded to each other with a carbon atom to which each is bonded to form divalent saturation having 4 to 20 carbon atoms. Alternatively, an unsaturated hydrocarbon group or a derivative thereof may be formed.

  Examples of the [E] acid diffusion inhibitor represented by the above formula include Nt-butoxycarbonyldi-n-octylamine, Nt-butoxycarbonyldi-n-nonylamine, Nt-butoxycarbonyldi- n-decylamine, Nt-butoxycarbonyldicyclohexylamine, Nt-butoxycarbonyl-1-adamantylamine, Nt-butoxycarbonyl-2-adamantylamine, Nt-butoxycarbonyl-N-methyl-1- Adamantylamine, (S)-(−)-1- (t-butoxycarbonyl) -2-pyrrolidinemethanol, (R)-(+)-1- (t-butoxycarbonyl) -2-pyrrolidinemethanol, Nt -Butoxycarbonyl-4-hydroxypiperidine, Nt-amyloxycarbonyl-4-hydroxypiperidine , Nt-butoxycarbonylpyrrolidine, N, N′-di-t-butoxycarbonylpiperazine, N, N-di-t-butoxycarbonyl-1-adamantylamine, Nt-butoxycarbonyl-4,4 ′ -Diaminodiphenylmethane, 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-butoxycarbonyl-1,9-diaminononane, N, N'- Di-t-butoxycarbonyl-1,10-diaminodecane, N, N′-di-t-butoxycarbonyl-1,12-diaminododeca N, N′-di-t-butoxycarbonyl-4,4′-diaminodiphenylmethane, Nt-butoxycarbonylbenzimidazole, Nt-butoxycarbonyl-2-methylbenzimidazole, Nt-butoxycarbonyl- Examples thereof include Nt-alkylalkoxycarbonyl group-containing amino compounds such as 2-phenylbenzimidazole.

  [E] In addition to the compound represented by the above formula, examples of the acid diffusion inhibitor include tertiary amine compounds, quaternary ammonium hydroxide compounds, photodegradable base compounds, and other nitrogen-containing heterocyclic compounds.

Examples of tertiary amine compounds include triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine. , Tri (cyclo) alkylamines such as cyclohexyldimethylamine, dicyclohexylmethylamine, and tricyclohexylamine;
Fragrances such as aniline, N-methylaniline, N, N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, 4-nitroaniline, 2,6-dimethylaniline, 2,6-diisopropylaniline Group amines;
Alkanolamines such as triethanolamine and N, N-di (hydroxyethyl) aniline;
N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetrakis (2-hydroxypropyl) ethylenediamine, 1,3-bis [1- (4-aminophenyl) -1- Methylethyl] benzenetetramethylenediamine, bis (2-dimethylaminoethyl) ether, bis (2-diethylaminoethyl) ether and the like.

  Examples of the quaternary ammonium hydroxide compound include tetra-n-propylammonium hydroxide and tetra-n-butylammonium hydroxide.

  [E] The content ratio of the acid diffusion inhibitor is preferably 10 parts by mass or less, and more preferably 8 parts by mass or less with respect to 100 parts by mass of [A] polysiloxane. When the amount used exceeds 10 parts by mass, the sensitivity as a resist tends to decrease.

<[F] polymer>
The negative radiation sensitive composition may further contain a [F] polymer. The negative radiation-sensitive composition contains the [F] polymer, so that the hydrophobicity of the resist film is improved, and even when immersion exposure is performed without the resist protective film, the material elution suppression is excellent. The usefulness of the mold radiation sensitive composition for immersion exposure increases.

[F] As an aspect of the polymer, for example, a structure in which a fluorinated alkyl group is bonded to the main chain;
A structure in which a fluorinated alkyl group is bonded to the side chain;
Examples include a structure in which a fluorinated alkyl group is bonded to the main chain and the side chain.

  As a monomer that gives a structure in which a fluorinated alkyl group is bonded to the main chain, for example, an α-trifluoromethyl acrylate compound, a β-trifluoromethyl acrylate compound, an α, β-trifluoromethyl acrylate compound, one or more types Examples thereof include compounds in which the hydrogen at the vinyl moiety is substituted with a fluorinated alkyl group such as a trifluoromethyl group.

  Monomers that give a structure in which a fluorinated alkyl group is bonded to the side chain include, for example, those in which the side chain of an alicyclic olefin compound such as norbornene is a fluorinated alkyl group or a derivative thereof, acrylic acid or methacrylic acid side Examples thereof include ester compounds in which the chain is a fluorinated alkyl group or a derivative thereof, and one or more olefin side chains (sites not including a double bond) being a fluorinated alkyl group or a derivative thereof.

  Examples of the monomer that gives a structure in which a fluorinated alkyl group is bonded to the main chain and the side chain include α-trifluoromethylacrylic acid, β-trifluoromethylacrylic acid, α, β-trifluoromethylacrylic acid, and the like. Is a fluorinated alkyl group or its derivative ester compound. One or more vinyl moiety hydrogens are substituted with a fluorinated alkyl group such as a trifluoromethyl group. The hydrogen bonded to the double bond of one or more alicyclic olefin compounds is replaced with a fluorinated alkyl group such as a trifluoromethyl group, and the side chain is a fluorinated alkyl group or a derivative thereof. And the like. In addition, an alicyclic olefin compound shows the compound in which a part of ring is a double bond.

  [F] The polymer is composed of the (f1) structural unit represented by the above formula (3), the (f2) structural unit represented by the above formula (4), and the (f3) structural unit represented by the above formula (5). It is preferable to have at least one structural unit selected from the group, and it may have “other structural units” other than these structural units. Hereinafter, each structural unit will be described in detail.

[(F1) structural unit]
(F1) The structural unit is a structural unit represented by the above formula (3).

In formula (3), R ¹² represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group. R ¹³ is a C 1-6 linear or branched alkyl group having a fluorine atom, or a C 4-20 monovalent alicyclic hydrocarbon group having a fluorine atom. However, in the alkyl group and alicyclic hydrocarbon group, part or all of the hydrogen atoms may be substituted.

  As said C1-C6 linear or branched alkyl group, a methyl group, an ethyl group, a propyl group, a butyl group etc. are mentioned, for example.

  Examples of the monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms include a cyclopentyl group, a cyclopentylpropyl group, a cyclohexyl group, a cyclohexylmethyl group, a cycloheptyl group, a cyclooctyl group, and a cyclooctylmethyl group.

  (F1) Monomers that give structural units include, for example, trifluoromethyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, perfluoroethyl (meth) acrylate, perfluoro n-propyl ( (Meth) acrylate, perfluoro i-propyl (meth) acrylate, perfluoro n-butyl (meth) acrylate, perfluoro i-butyl (meth) acrylate, perfluoro t-butyl (meth) acrylate, perfluorocyclohexyl (meth) Acrylate, 2- (1,1,1,3,3,3-hexafluoro) propyl (meth) acrylate, 1- (2,2,3,3,4,4,5,5-octafluoro) pentyl ( (Meth) acrylate, 1- (2,2,3,3,4,4,5,5-octafluoro) hex (Meth) acrylate, perfluorocyclohexylmethyl (meth) acrylate, 1- (2,2,3,3,3-pentafluoro) propyl (meth) acrylate, 1- (2,2,3,3,4, 4,4-Heptafluoro) penta (meth) acrylate, 1- (3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10- Heptadecafluoro) decyl (meth) acrylate, 1- (5-trifluoromethyl-3,3,4,4,5,6,6,6-octafluoro) hexyl (meth) acrylate and the like.

  Examples of the structural unit (f1) include structural units represented by the following formulas (3-1) and (3-2).

（式（３−１）及び（３−２）中、Ｒ^１２は上記式（３）と同義である。）

(In the formulas (3-1) and (3-2), R ¹² has the same meaning as the above formula (3).)

  In the [F] polymer, the content of the (f1) structural unit is preferably 10 mol% to 70 mol%, and 20 mol% to 50 mol% with respect to all the structural units constituting the [F] polymer. More preferred. In addition, the [F] polymer may have 1 type (s) or 2 or more types of (f1) structural units.

[(F2) Structural unit]
(F2) The structural unit is a structural unit represented by the above formula (4).

In the formula (4), R ¹⁴ is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group. R ¹⁵ is a (k + 1) -valent linking group. X ³ is a divalent linking group having a fluorine atom. R ¹⁶ is a hydrogen atom or a monovalent organic group. k is an integer of 1 to 3. However, ^{if X 3} and ^{R 16} there are a plurality, a plurality of ^{X 3} and ^{R 16} may be the same or different.

In the above formula (4), the (k + 1) -valent linking group represented by R ¹⁵ is, for example, a linear or branched hydrocarbon group having 1 to 30 carbon atoms or an alicyclic hydrocarbon having 3 to 30 carbon atoms. A group, an aromatic hydrocarbon group having 6 to 30 carbon atoms, or one or more groups selected from the group consisting of these groups and an oxygen atom, a sulfur atom, an ether group, an ester group, a carbonyl group, an imino group, and an amide group And a combination of these. The (k + 1) -valent linking group may have a substituent.

  Examples of the linear or branched hydrocarbon group having 1 to 30 carbon atoms include (k + 1) hydrocarbon groups such as methane, ethane, propane, butane, pentane, hexane, heptane, decane, icosane and triacontane. And a group in which a hydrogen atom is removed.

Examples of the alicyclic hydrocarbon group having 3 to 30 carbon atoms include monocyclic saturated hydrocarbons such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclodecane, methylcyclohexane, and ethylcyclohexane;
Monocyclic unsaturated hydrocarbons such as cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclodecene, cyclopentadiene, cyclohexadiene, cyclooctadiene, cyclodecadiene;
Bicyclo [2.2.1] heptane, bicyclo [2.2.2] octane, tricyclo [5.2.1.0 ^2,6 ] decane, tricyclo [3.3.1.1 ^3,7 ] decane, Tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] polycyclic saturated hydrocarbons such as dodecane and adamantane;
Bicyclo [2.2.1] heptene, bicyclo [2.2.2] octene, tricyclo [5.2.1.0 ^2,6 ] decene, tricyclo [3.3.1.1 ^3,7 ] decene, Tetracyclo [6.2.1.1 ^3,6 . And a group obtained by removing (k + 1) hydrogen atoms from a polycyclic hydrocarbon group such as 0 ^2,7 ] dodecene.

  Examples of the aromatic hydrocarbon group having 6 to 30 carbon atoms include aromatic hydrocarbon groups such as benzene, naphthalene, phenanthrene, anthracene, tetracene, pentacene, pyrene, picene, toluene, xylene, ethylbenzene, mesitylene, cumene, and the like (k + 1). ) Groups from which a single hydrogen atom has been removed.

In the above formula (4), examples of the divalent linking group having a fluorine atom represented by X ³ include a C 1-20 divalent linear hydrocarbon group having a fluorine atom. Examples of X ³ include structures represented by the following formulas (X ³ -1) to (X ³ -6).

X ³ is preferably a structure represented by the above formulas (X ³ -1) and (X ³ -2).

In the above formula (4), examples of the organic group represented by R ¹⁶ include a linear or branched hydrocarbon group having 1 to 30 carbon atoms, an alicyclic hydrocarbon group having 3 to 30 carbon atoms, and 6 carbon atoms. To 30 aromatic hydrocarbon groups, or a combination of these groups and one or more groups selected from the group consisting of oxygen, sulfur, ether, ester, carbonyl, imino and amide groups Is mentioned.

  Examples of the structural unit (f2) include structural units represented by the following formulas (4-1) and (4-2).

（式（４−１）中、Ｒ^１５は炭素数１〜２０の２価の直鎖状、分岐状又は環状の飽和若しくは不飽和の炭化水素基である。Ｒ^１４、Ｘ^３及びＲ^１６は上記式（４）と同義である。
式（５−２）中、Ｒ^１４、Ｘ^３、Ｒ^１６及びｋは上記式（４）と同義である。但し、ｋが２又は３の場合、複数のＸ^３及びＲ^１６はそれぞれ同一であっても異なっていてもよい。）

(In the formula (4-1), R ¹⁵ is a divalent linear, branched or cyclic saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms. R ¹⁴ , X ³ and R ¹⁶ are It is synonymous with said Formula (4).
In formula (5-2), R < ¹⁴ >, X < ³ >, R < ¹⁶ > and k are synonymous with said formula (4). However, when k is 2 or 3, the plurality of X ³ and R ¹⁶ may be the same or different. )

  Examples of the structural unit represented by the above formula (4-1) and formula (4-2) include the following formula (4-1-1), formula (4-1-2), and formula (4-2-1). The structural unit shown by these is mentioned.

（式（４−１−１）、（４−１−２）及び（４−２−１）中、Ｒ^１４は上記式（４）と同義である。）

(In the formulas (4-1-1), (4-1-2) and (4-2-1), R ¹⁴ has the same meaning as the above formula (4).)

  (F2) Examples of monomers that give structural units include (meth) acrylic acid (1,1,1-trifluoro-2-trifluoromethyl-2-hydroxy-3-propyl) ester, (meth) acrylic acid (1,1,1-trifluoro-2-trifluoromethyl-2-hydroxy-4-butyl) ester, (meth) acrylic acid (1,1,1-trifluoro-2-trifluoromethyl-2-hydroxy -5-pentyl) ester, (meth) acrylic acid (1,1,1-trifluoro-2-trifluoromethyl-2-hydroxy-4-pentyl) ester, (meth) acrylic acid 2-{[5- ( 1 ′, 1 ′, 1′-trifluoro-2′-trifluoromethyl-2′-hydroxy) propyl] bicyclo [2.2.1] heptyl} ester and the like.

  In the [F] polymer, the content of the (f2) structural unit is preferably 20 mol% to 80 mol%, more preferably 30 mol% to 70 mol%, based on all structural units constituting the [F] polymer. More preferred. In addition, the [F] polymer may have 1 type or 2 types or more of (f2) structural units.

[(F3) Structural unit]
(F3) The structural unit is a structural unit represented by the above formula (5).

In the formula (5), R ¹⁷ is a linear or branched alkyl group having 1 to 6 carbon atoms having a fluorine atom, or a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms having a fluorine atom. It is. However, in the alkyl group and alicyclic hydrocarbon group, part or all of the hydrogen atoms may be substituted. c is an integer of 0-2. d is an integer of 0-4.

The linear or branched alkyl group having 1 to 6 carbon atoms, specific examples of the monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms, mentioned as examples of each group in the R ¹³ The thing similar to a thing is illustrated.

  Examples of the structural unit (f3) include a structural unit represented by the following formula (5-1).

  In the [F] polymer, the content of the (f3) structural unit is preferably 10 mol% to 50 mol%, and 20 mol% to 40 mol% with respect to all the structural units constituting the [F] polymer. More preferred. In addition, the [F] polymer may have 1 type (s) or 2 or more types of (f3) structural units.

[Other structural units]
[F] The polymer may further have one or more structural units including a lactone structure, a structural unit including an alicyclic structure, and the like as “other structural units”.

  In the [F] polymer, the content of other structural units is usually 90 mol% or less, preferably 20 mol% to 80 mol%, based on all the structural units constituting the [F] polymer, 30 More preferred is mol% to 70 mol%. In addition, the [F] polymer may have 1 type, or 2 or more types of another structural unit.

  [F] As a compounding quantity of a polymer, 0.1 mass part-20 mass parts are preferable with respect to 100 mass parts of [A] polysiloxane, and 1 mass part-15 mass parts are more preferable. If it is less than 0.1 part by mass, the effect of containing the [F] polymer may not be sufficient. On the other hand, when the amount exceeds 20 parts by mass, the water repellency of the resist surface becomes too high and development failure may occur.

  [F] The fluorine atom content in the polymer is preferably larger than that of [A] polysiloxane. [F] The content ratio of fluorine atoms in the polymer is usually 5% by mass or more, preferably 5% by mass to 50% by mass, more preferably 5%, based on 100% by mass of the total amount of the [F] polymer. It is mass%-45 mass%. This fluorine atom content ratio can be measured by fluorescent X-ray spectroscopy. When the fluorine atom content in the [F] polymer is larger than that of the [A] polysiloxane, the photo formed by the negative radiation-sensitive composition containing the [F] polymer and the [A] polysiloxane. The water repellency of the resist film surface can be increased, and there is no need to separately form an upper layer film during immersion exposure. In order to sufficiently exhibit the above effect, the difference between the fluorine atom content in the [A] polysiloxane and the fluorine atom content in the [F] polymer is 1% by mass or more. Preferably, it is 5 mass% or more.

<[F] Polymer Synthesis Method>
[F] The polymer can be produced, for example, by polymerizing a monomer corresponding to each predetermined structural unit in a suitable solvent using a radical polymerization initiator.

Examples of the solvent used for the polymerization include alkanes such as n-pentane, n-hexane, n-heptane, n-octane, n-nonane, and n-decane;
Cycloalkanes such as cyclohexane, cycloheptane, cyclooctane, decalin, norbornane;
Aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene;
Halogenated hydrocarbons such as chlorobutanes, bromohexanes, dichloroethanes, hexamethylene dibromide, chlorobenzene;
Saturated carboxylic acid esters such as ethyl acetate, n-butyl acetate, i-butyl acetate and methyl propionate;
Ketones such as acetone, 2-butanone, 4-methyl-2-pentanone, 2-heptanone;
Ethers such as tetrahydrofuran, dimethoxyethanes, diethoxyethanes;
Examples include alcohols such as methanol, ethanol, 1-propanol, 2-propanol, and 4-methyl-2-pentanol. These solvents may be used alone or in combination of two or more.

  As reaction temperature in the said superposition | polymerization, 40 to 150 degreeC and 50 to 120 degreeC are preferable normally. The reaction time is usually preferably 1 hour to 48 hours and 1 hour to 24 hours.

  [F] The Mw of the polymer is preferably 1,000 to 50,000, more preferably 1,000 to 40,000, and particularly preferably 1,000 to 30,000. [F] When the Mw of the polymer is less than 1,000, a sufficient receding contact angle cannot be obtained. On the other hand, when Mw exceeds 50,000, the developability of the resist tends to decrease.

  [F] The ratio (Mw / Mn) of Mw of the polymer to the number average molecular weight (Mn) in terms of polystyrene by GPC method is preferably 1 to 5, and more preferably 1 to 4.

<Other optional components>
The said negative radiation sensitive composition can contain surfactant, a sensitizer, etc. in the range which does not impair the effect of this invention. Hereinafter, these other optional components will be described in detail. These other optional components can be used alone or in admixture of two or more. Moreover, the compounding quantity of another arbitrary component can be suitably determined according to the objective.

[Surfactant]
Surfactants are components that have the effect of improving coatability, striation, developability, and the like. Examples of the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene n-octylphenyl ether, polyoxyethylene n-nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol diacrylate. In addition to nonionic surfactants such as stearate, the following trade names are KP341 (Shin-Etsu Chemical Co., Ltd.), Polyflow No. 75, no. 95 (above, Kyoeisha Chemical Co., Ltd.), Ftop EF301, EF303, EF352 (above, Tochem Products), MegaFuck F171, F173 (above, Dainippon Ink and Chemicals), Florard FC430, FC431 ( Sumitomo 3M), Asahi Guard AG710, Surflon S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106 (above, Asahi Glass Co., Ltd.) ) And the like.

[Sensitizer]
The sensitizer absorbs radiation energy and transmits the energy to the [B] acid generator and [C] base generator, thereby increasing the amount of acid / base generated. It has the effect of improving the “apparent sensitivity” of the negative radiation sensitive composition. Examples of the sensitizer include carbazoles, acetophenones, benzophenones, naphthalenes, phenols, biacetyl, eosin, rose bengal, pyrenes, anthracenes, phenothiazines and the like.

<Preparation of negative radiation-sensitive composition>
The negative radiation sensitive composition is, for example, the above [A] polysiloxane, [B] acid generator, [C] base generator, and [E] acid diffusion in the above [D] solvent, if necessary. It can be prepared by mixing the inhibitor, the [F] polymer and other optional components at a predetermined ratio. The organic solvent is not particularly limited as long as it is exemplified as the above [D] solvent and can dissolve or disperse [A] polysiloxane, [B] acid generator and the like. The negative radiation-sensitive composition is usually used after being dissolved in the solvent [D] so that the total solid content concentration is 1% by mass to 50% by mass, preferably 2% by mass to 25% by mass. For example, it is prepared by filtering with a filter having a pore diameter of about 0.2 μm.

<Pattern formation method>
The pattern forming method of the present invention comprises:
(1) Using the negative radiation-sensitive composition, a step of forming a coating film on a substrate (hereinafter sometimes referred to as “(1) step”),
(2) a step of exposing the coating film (hereinafter sometimes referred to as “(2) step”),
(3) a step of heating the exposed coating film (hereinafter sometimes referred to as “(3) step”), and (4) a step of developing the heated coating film with a developer (hereinafter referred to as “ (Sometimes referred to as (4) process)
including.

  According to the formation method, a negative radiation-sensitive composition that can form a fine resist pattern and satisfies lithography characteristics such as LWR can be provided. Hereinafter, each process is explained in full detail.

[(1) Process]
In this process, a negative radiation sensitive composition or a composition solution obtained by dissolving it in a solvent is applied to silicon wafers, silicon dioxide, antireflection by coating means such as spin coating, cast coating, roll coating, etc. A coating film is formed by applying a predetermined film thickness on a substrate such as a wafer coated with a film, and then volatilizing the solvent in the coating film by pre-baking.

[(2) Process]
In this step, the coating film formed in step (1) is exposed to radiation (in some cases, through an immersion medium such as water) and exposed. At this time, radiation is irradiated through a mask having a predetermined pattern. As the radiation, irradiation is performed by appropriately selecting from visible light, ultraviolet light, far ultraviolet light, X-rays, charged particle beams and the like according to the line width of the target pattern. Far ultraviolet rays represented by ArF excimer laser (wavelength 193 nm) and KrF excimer laser (wavelength 248 nm) are preferable for obtaining a fine pattern, and ArF excimer laser is more preferable. The amount of exposure is appropriately selected depending on the type and amount of the [B] acid generator and [C] base generator used, but is preferably 5 to 100 mJ / cm ² .

[(3) Process]
In this step, the coating film exposed in step (2) is heated, that is, post-exposure bake (PEB), so that the polysiloxane produced by the acid generated from the [B] acid generator in the exposed portion of the coating film A cross-linking reaction is caused. PEB is normally selected and carried out in the range of 50 ° C to 180 ° C.

[(4) Process]
In this step, a predetermined photoresist pattern is formed by developing the coating film heated in step (3) with a developer. After development, it is common to wash with water and dry. As the developer, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, ethyl Dimethylamine, triethanolamine, tetramethylammonium hydroxide, pyrrole, piperidine, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1,5-diazabicyclo- [4.3.0] An aqueous alkaline solution in which at least one alkaline compound such as -5-nonene is dissolved is preferable.

  When performing immersion exposure, before the step (2), in order to protect the direct contact between the immersion liquid and the resist film, an immersion liquid insoluble immersion protective film is formed on the resist film. It may be provided. As the immersion protective film, a solvent-removable protective film that is peeled off by a solvent before the step (3) (see, for example, JP-A-2006-227632), and a developer peeling that peels off simultaneously with the development in the step (4) Any of the mold protective films (for example, refer to WO2005-069096 and WO2006-035790) may be used. However, from the viewpoint of throughput, it is preferable to use a developer peeling type immersion protective film.

<Insulating film manufacturing method>
The manufacturing method of the insulating film of the present invention is as follows:
(1) Using the negative radiation sensitive composition, a step of forming a coating film on a substrate,
(2) a step of exposing the coating film,
(3) a step of heating the exposed coating film;
(4) A step of developing the heated coating film with a developer, and (5) A step of performing a curing treatment by irradiation with high energy rays and / or heating (hereinafter sometimes referred to as “(5) step”).
including.

  Since the details of the steps (1) to (4) are the same as the contents described in the above-mentioned pattern forming method, the description is omitted here.

[(5) Process]
In this step, the resist pattern is cured by irradiation with high energy rays and / or heating to form a cured pattern. The cured product formed from the manufacturing method can be used as an insulator or the like, and is suitable as a patterned wiring insulator that requires extremely fine patterning performance, an inorganic sacrificial film for processing semiconductor materials, or the like. is there.

  Examples of the curing treatment include a method of curing in a UV cure apparatus (RapidCure FC, Axelis) at 400 ° C. in air for 5 minutes.

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

<[A] Synthesis of polysiloxane>
[Synthesis Example 1]
Into a quartz three-neck flask purged with nitrogen, 1.28 g of 20% oxalic acid aqueous solution and 83.53 g of ultrapure water were added and heated to 65 ° C. Next, a solution in which 142.07 g (1.043 mol) of methyltrimethoxysilane and 23.14 g of ethoxypropanol were mixed was added dropwise to the reaction vessel over 1 hour, followed by stirring at 65 ° C. for 4 hours. The reaction solution was returned to room temperature and concentrated under reduced pressure until the solid content concentration became 25% to obtain a solution of a polysiloxane polymer (A-1) represented by the following formula. Mw was 6,500.

[Synthesis Example 2]
Into a nitrogen-substituted quartz three-necked flask, 1.33 g of a 20% maleic acid aqueous solution and 86.16 g of ultrapure water were added and heated to 65 ° C. Next, a solution in which (a) 16.04 g (0.105 mol) of tetramethoxysilane, 129.22 g (0.949 mol) of methyltrimethoxysilane, and 16.19 g of ethoxypropanol was added over 1 hour. The solution was added dropwise to the reaction vessel and stirred at 65 ° C. for 4 hours. The reaction solution was returned to room temperature and concentrated under reduced pressure until the solid content concentration became 25% to obtain a solution of a polysiloxane polymer (A-2) represented by the following formula. Mw was 8,800. As a result of ²⁹ Si-NMR analysis, the constituent monomer ratio (a) :( b) of the polysiloxane polymer (A-2) was 10:90 (mol%). ²⁹ Si-NMR analysis was measured using AVANCE III AV400N (manufactured by Bruker).

[Synthesis Example 3]
In a three-necked flask made of nitrogen-substituted quartz, 0.31 g of trifluoroacetic acid, 14.85 g of ultrapure water and 22.26 g of ethoxypropanol were added and heated to 55 ° C. Next, a solution prepared by mixing (a) 10.92 g of tetramethoxysilane, (b) 35.56 g of phenyltrimethoxysilane, (c) 34.49 g of triethoxysilyloxetane, and 81.61 g of ethoxypropanol was reacted over 1 hour. The solution was dropped into a container and stirred at 55 ° C. for 4 hours. The reaction solution was returned to room temperature and concentrated under reduced pressure until the solid content concentration became 25% to obtain a solution of a polysiloxane polymer (A-3) represented by the following formula. Mw was 10,200. As a result of ¹³ C-NMR and ²⁹ Si-NMR analysis, the constituent monomer ratio (a) :( b) :( C) of the polysiloxane polymer (A-3) was 20:50:30 (mol%). there were.

[Synthesis Example 4]
Into a nitrogen-substituted quartz three-necked flask, 1.52 g of a 20% maleic acid aqueous solution and 99.26 g of ultrapure water were added and heated to 75 ° C. Next, a solution in which (a) 107.08 g (0.703 mol) of tetramethoxysilane, 41.07 g (0.302 mol) of methyltrimethoxysilane, and 1.07 g of ethoxypropanol was added over 1 hour. The solution was added dropwise to the reaction vessel and stirred at 55 ° C. for 2 hours. The reaction solution was returned to room temperature and concentrated under reduced pressure until the solid content concentration became 25% to obtain a solution of a polysiloxane polymer (A-4) represented by the following formula. Mw was 11,800. As a result of ²⁹ Si-NMR analysis, the constituent monomer ratio (a) :( b) of the polysiloxane polymer (A-4) was 70:30 (mol%).

[Synthesis Example 5]
Into a nitrogen-substituted quartz three-necked flask, 1.32 g of 20% maleic acid aqueous solution and 86.27 g of ultrapure water were added and heated to 75 ° C. Next, (a) 30.74 g (0.202 mol) of tetramethoxysilane, (b) 68.78 g (0.505 mol) of methyltrimethoxysilane, (c) 44.91 g (0.303 mol) of vinyltrimethoxysilane ) And 17.97 g of ethoxypropanol were added dropwise to the reaction vessel over 1 hour and stirred at 65 ° C. for 3 hours. This reaction liquid was returned to room temperature and concentrated under reduced pressure until the solid content concentration became 25%, to obtain a solution of a polysiloxane polymer (A-5) represented by the following formula. Mw was 4,100. As a result of ¹³ C-NMR and ²⁹ Si-NMR analysis, the constituent monomer ratio (a) :( b) :( c) of the polysiloxane polymer (A-5) was 20:50:30 (mol%). there were.

[Synthesis Example 6]
Into a nitrogen-substituted quartz three-necked flask, 1.28 g of a 20% maleic acid aqueous solution and 83.75 g of ultrapure water were added and heated to 65 ° C. Next, (a) 33.71 g (0.095 mol) of 1,2-bis (triethoxysilyl) ethane, (b) 116.56 g (0.856 mol) of methyltrimethoxysilane, and 14.70 g of ethoxypropanol were added. The mixed solution was dropped into the reaction vessel over 1 hour and stirred at 55 ° C. for 4 hours. This reaction liquid was returned to room temperature and concentrated under reduced pressure until the solid content concentration became 25% to obtain a solution of a polysiloxane polymer (A-6) represented by the following formula. Mw was 4,800. As a result of ²⁹ Si-NMR analysis, the constituent monomer ratio (a) :( b) of the polysiloxane polymer (A-6) was 10:90 (mol%).

<Synthesis of [F] polymer>
The monomer used for the synthesis of [F] polymer is shown below.

[Synthesis Example 7]
40 mol% of the compound (M-1) and 60 mol% of the compound (M-2) are dissolved in 50 g of methyl ethyl ketone, and further 1.38 g of dimethyl-2,2′-azobisisobutyrate) azobisisobutyronitrile. A monomer solution charged with (8 mol%) was prepared. The total amount of monomers at the time of preparation was 50 g. In addition, mol% of each monomer represents mol% with respect to the total amount of monomer, and mol% of initiator represents mol% with respect to the total amount of monomer and initiator. On the other hand, 50 g of ethyl methyl ketone was added to a 500 mL three-necked flask equipped with a thermometer and a dropping funnel, and purged with nitrogen for 30 minutes. Then, it heated so that it might become 80 degreeC, stirring the inside of a flask with a magnetic stirrer. Subsequently, the said monomer solution was dripped over 3 hours using the dropping funnel in the flask. After dropping, the mixture was aged for 3 hours, and then cooled to 30 ° C. or lower to obtain a copolymer solution. Next, the copolymer solution was poured into methanol having 5 times the mass of the reaction solution, stirred for 30 minutes, filtered, and washed twice in 200 mL of methanol to obtain a solution of copolymer (F-1). Got. Mw was 6,600 and the yield was 49% by mass. As a result of ¹³ C-NMR analysis, the constituent monomer ratio of (M-1) and (M-2) in the copolymer (F-1) was 38:62 (mol%).

[Synthesis Examples 8 to 12]
A [F] polymer was synthesized in the same manner as in Synthesis Example 1 except that the types and amounts of monomers shown in Table 1 were used. In Table 1, “-” indicates that the corresponding component was not used. Table 1 also shows the Mw, yield, and content ratio of each structural unit of each [F] polymer.

[Synthesis Example 13]
Into a nitrogen-substituted quartz three-necked flask, 0.84 g of 20% maleic acid aqueous solution and 54.92 g of ultrapure water were added and heated to 65 ° C. Next, a solution in which 19.57 g (0.129 mol) of (a) tetramethoxysilane, 91.64 g (0.514 mol) of trifluoromethyltrimethoxysilane, and 83.03 g of ethoxypropanol were mixed for 1 hour. The solution was added dropwise to the reaction vessel and stirred at 65 ° C. for 4 hours. The reaction solution was returned to room temperature and concentrated under reduced pressure until the solid content concentration became 25% to obtain a solution of a copolymer (F-7). Mw was 7,700 and the yield was 97% by mass. As a result of ²⁹ Si-NMR analysis, the constituent monomer ratio of (a) and (b) in the copolymer (F-7) was 20:80 (mol%).

<Preparation of negative radiation-sensitive composition>
[Example 1]
[A] The polysiloxane solution is taken in an amount corresponding to 100 parts by mass of [A] polysiloxane, and [B] (B-1) as an acid generator is 2 parts by mass, and [C] a base generator. A negative radiation sensitive composition was prepared by mixing 10 parts by weight of (C-1) and 0.4 part by weight of (E-1) as an [E] acid diffusion controller. In addition, propylene glycol monomethyl ether acetate was added as a solvent [D] so as to obtain a solid concentration suitable for obtaining a desired film thickness.

[Examples 2 to 14 and Comparative Examples 1 to 4]
A negative radiation-sensitive composition was prepared in the same manner as in Example 1 except that the types and amounts of each component shown in Table 2 were used. In Table 1, “-” indicates that the corresponding component was not used. Details of each component used in Examples and Comparative Examples are shown below.

<[B] Acid generator>
B-1: Triphenylsulfonium nonafluoro-n-butanesulfonate B-2: Compound represented by the following formula

<[C] Base generator>
C-1: Compound represented by the following formula C-2: 2-nitrobenzylcyclohexyl carbamate

<[E] acid diffusion inhibitor>
E-1: 1-tert-butoxycarbonyl-2-phenylbenzimidazole

<Pattern formation>
On a silicon wafer coated with antireflection film ARF29A (Nissan Chemical Co., Ltd.), negative radiation sensitive compositions prepared as examples and comparative examples were applied using a spin coater and pre-baked at the temperatures and times shown in Table 3. Then, a coating film was formed. Subsequently, the obtained coating film was exposed, post-baked, developed and rinsed at the temperatures and times shown in Table 3 to form a pattern. The film thickness (nm) of the formed coating film is also shown in Table 3.

Details of the equipment used in the exposure type and development and rinsing steps in Table 3 are shown below.
Exposure was carried out variables in the range of ^{10mJ / cm 2 ~30mJ / cm 2} .
KrF: Using a mask that forms a pattern with a 500 nm pitch and 250 nm line width, exposure is NA = 0.68, NIKON, S203B is used, film formation, development, and rinsing are CLEAN TRACK ACT-8 (Tokyo Electron) ArF used: A mask that forms a pattern with a 180 nm pitch and a 90 nm line width is used. Exposure is NA = 0.78, NIKON, S306C is used, film formation, development, and rinsing are CLEAN TRACK ACT-8 (Tokyo Electron) ArF-i: Using a mask that forms a pattern with a 90 nm pitch and 45 nm line width, exposure is NA = 1.35 (using NIKON, S610, film formation, development, rinsing is CLEAN TRACK LITHIUS Pro-i ( Tokyo Electron)

<Evaluation of pattern>
The shape of the obtained pattern was confirmed using a scanning electron microscope (S-9380, Hitachi High-Technologies Corporation). The exposure condition where the largest number of line patterns are formed is set as the best condition, and the pattern formation rate (%), line pattern width (nm), and LWR (line pattern width Roughness variation (nm) was measured. The results are shown in Table 3.

  The pattern formation rate refers to the ratio of the number of resist line patterns formed when the number of line patterns formed on the mask is 100. When the pattern formation rate exceeded 100% and the line pattern width was smaller than the mask size, it was determined that a desired pattern was obtained. Further, LWR was judged to be good if it was 10% or less of the line width.

<Manufacture of insulating film>
The patterns of Examples 5 and 14 were treated in a UV cure apparatus (RapidCure FC, Axelis) at 400 ° C. in air for 5 minutes to produce an insulating film.

<Evaluation of insulating film>
When the shape change of the cured product (cured pattern) before and after the treatment was examined with a scanning electron microscope, no deformation of the pattern was observed in any sample, and it was found that the size contracted by 10% in both the width and height directions. It was. At this time, when the shrinkage rate is 15% or less, the influence on the warp of the substrate, the disconnection of the pattern, the intersection (bridge), and the dropout is small and good. Further, the composition of Example 5 was applied to a Si wafer and similarly fired with a UV curing device to obtain a fired film similar to the above pattern. When the dielectric constant of the film was measured using an LCR meter, room temperature (25 ° C) measurement was 2.9, and 130 ° C measurement was 2.6. Similarly, the measured dielectric constant of the fired film formed using the composition of Example 14 was 2.6 at both room temperature and 130 ° C. Thus, since the fired film has a low dielectric constant of 3 or less and a small leakage current, it can be said to be good as a low dielectric constant insulating film. Note that the difference in dielectric constant between room temperature and 130 ° C. is an indicator of the hygroscopicity of the material, and the smaller the difference, the lower the hygroscopicity and the better the reliability as a permanent film. Further, when the leakage current was measured by applying a voltage of 2 megavolts, Example 5 was 9.3 × 10 ⁻⁹ A / cm ² , and Example 14 was 7.5 × 10 ⁻⁹ A / cm ² . The performance was sufficient.

  From Table 3, the negative radiation-sensitive composition of the present invention achieves a good pattern formation rate of 140 to 180% in any exposure type of ArF, ArF-i, and KrF, and the lines of each example. It became clear that a fine pattern having a pattern width of about ½ or less of each mask pattern can be formed. That is, it was confirmed that the negative radiation-sensitive composition can form a fine pattern divided into two at the center line vicinity in one line-shaped exposed portion. It was also found that LWR was good and that the lithography characteristics were also excellent.

  The present invention can provide a negative radiation-sensitive composition capable of forming a fine resist pattern and satisfying lithography properties such as LWR, and a pattern forming method using such a composition. Further, the cured product of the obtained pattern is suitable as an insulating film such as a patterned wiring insulator or an inorganic sacrificial film for processing a semiconductor material that requires extremely fine patterning performance.

Claims (9)

[A] polysiloxane,
[B] a radiation sensitive acid generator,
[C] A radiation-sensitive base generator, and [D] a negative radiation-sensitive composition containing a solvent.   [B] The negative radiation-sensitive composition according to claim 1, wherein the ratio of the equivalent of the [C] base generator to the equivalent of the acid generator is 0.1 or more and 100 or less.   The negative radiation-sensitive composition according to claim 1 or 2, wherein [B] the acid generator is an onium salt compound, and [C] the base generator is a nitrogen-containing compound. [A] The negative radiation-sensitive composition according to claim 1, 2, or 3, wherein the polysiloxane has a structural unit derived from a hydrolyzable silane compound represented by the following formula (1).

(In the formula (1), a is .R ¹ is an integer of 0 to 3 is a monovalent organic group. However, ^{if R 1} there are a plurality, the plurality of ^{R 1} may be the same or different and which may .X ¹ is chlorine atom, a bromine atom or oR ² .R ² is a monovalent organic group. However, when ^{the X 1} there are a plurality, the plurality of ^{X 1} are the same or different May be good.)   [E] The negative radiation-sensitive composition according to any one of claims 1 to 4, further comprising an acid diffusion inhibitor.   [F] The negative radiation-sensitive composition according to any one of claims 1 to 5, further comprising a polymer having a fluorine atom. [F] The polymer according to claim 6, wherein the polymer has at least one structural unit selected from the group consisting of a plurality of structural units represented by the following formula (3), formula (4) and formula (5). The negative radiation sensitive composition as described.

(In Formula (3), R ¹² is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. R ¹³ is a C 1-6 linear or branched alkyl group having a fluorine atom. Or a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms having a fluorine atom, provided that the alkyl group and the alicyclic hydrocarbon group are partially or entirely substituted with hydrogen atoms. May be good.)

(In formula (4), R ¹⁴ is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group. R ¹⁵ is a (k + 1) -valent linking group. X ³ is a fluorine atom having 2 atoms. is a valence connecting group ^{.R 16} is .k a hydrogen atom or a monovalent organic group is an integer of 1 to 3. However, ^{if X 3} and ^{R 16} there are a plurality, a plurality of ^{X 3} And R ¹⁶ may be the same or different.)

(In the formula (5), R ¹⁷ is a linear or branched alkyl group having 1 to 6 carbon atoms having a fluorine atom, or a monovalent alicyclic hydrocarbon having 4 to 20 carbon atoms having a fluorine atom. Provided that the alkyl group and the alicyclic hydrocarbon group may be partially or entirely substituted with hydrogen atoms, c is an integer of 0 to 2, and d is 0 to 4; Is an integer.) (1) The process of forming a coating film on a board | substrate using the negative radiation sensitive composition of any one of Claims 1-7,
(2) a step of exposing the coating film,
(3) A pattern forming method including a step of heating the exposed coating film, and (4) a step of developing the heated coating film with a developer. (1) The process of forming a coating film on a board | substrate using the negative radiation sensitive composition of any one of Claims 1-7,
(2) a step of exposing the coating film,
(3) a step of heating the exposed coating film;
(4) A method for producing an insulating film, comprising a step of developing the heated coating film with a developer, and (5) a step of performing a curing treatment by irradiation with high energy rays and / or heating.