JP2010191297A - Negative radiation-sensitive composition, method for forming cured pattern, and cured pattern - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a negative radiation-sensitive composition suitable for forming a cured pattern that constitutes an interlayer insulating film low in dielectric constant, and to provide a method for forming a cured pattern using the composition, and a cured pattern obtained by the method for forming a cured pattern. <P>SOLUTION: The negative radiation-sensitive composition contains: [A] a polysiloxane having a silanol group; [B] a polymer having a structural unit expressed by general formula (1) and having a weight average molecular weight of 1,000 to 100,000; and [C] a solvent. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a negative radiation sensitive composition, a method for forming a cured pattern, and a cured pattern. More specifically, the present invention relates to a negative radiation-sensitive composition capable of forming a cured film having a low relative dielectric constant, a cured pattern using the same, and a method for forming the same.

Conventionally, a silica (SiO ₂ ) film formed by a vacuum process such as a CVD method has been frequently used as an interlayer insulating film in a semiconductor element or the like.
In recent years, for the purpose of forming an interlayer insulating film having a more uniform film thickness, a coating type insulating film called SOG (Spin on Glass) film, which is mainly composed of a hydrolysis product of tetraalkoxysilane, is also available. It is used (for example, refer patent document 1). In addition, with the high integration of semiconductor elements and the like, a low dielectric constant interlayer insulating film called polyorganosiloxane called organic SOG has been developed (see, for example, Patent Documents 2 and 3).

Japanese Patent Laid-Open No. 5-36684 Japanese Patent Laid-Open No. 2003-3120 JP 2005-213492 A

  However, with further higher integration and multi-layering of semiconductor elements and the like, better electrical insulation between conductors is required, and accordingly, an interlayer insulating film having a lower relative dielectric constant has been demanded. Yes.

The formation of the interlayer insulating film is usually performed by repeating the pattern transfer process. In general, first, many different mask material layers are formed on an interlayer insulating film layer, and a photosensitive resin composition is applied to the uppermost portion thereof. Next, after a desired circuit pattern is formed on the photosensitive resin composition film by reduction projection exposure and development, the pattern is transferred to the sequentially stacked mask material layers.
Finally, after the pattern is transferred from the mask material layer to the interlayer insulating film layer, the mask material layer is removed to form an interlayer insulating film. As described above, processing and formation of an interlayer insulating film that is generally performed is very time-consuming and is a very inefficient process, and thus an improvement method is required.

  The present invention has been made in view of the above circumstances, has a radiation-sensitive property, can be patterned, has a good resolution, and further achieves higher integration and multilayering of semiconductor elements and the like. And a negative radiation sensitive composition suitable for forming a cured pattern constituting an interlayer insulating film having a low relative dielectric constant, a cured pattern forming method using the same, and a cured pattern forming method obtained using the same It is an object to provide a cured pattern.

（式中、Ｒ^１は水素原子、メチル基又はトリフルオロメチル基を表し、Ｚは放射線により酸を発生する基を表す。）
２．上記一般式（１）で表される構造単位を有する重合体において、Ｚが放射線によりアニオンとなる基である上記１に記載のネガ型感放射線性組成物。
３．上記一般式（１）で表される構造単位が、下記一般式（２）で表される構造単位である上記１又は２に記載のネガ型感放射線性組成物。

（式中、Ｒ^１は水素原子、メチル基又はトリフルオロメチル基を表し、Ｒ^２は、それぞれ、独立に、水素原子、置換若しくは非置換の炭素数１〜１０の直鎖状あるいは分岐状のアルキル基、フッ素原子又は炭素数１〜１０の直鎖状若しくは分岐状のパーフルオロアルキル基を表し、Ａは単結合又は２価の有機基を表し、Ｇは単結合又はフッ素原子を含む２価の有機基を表し、Ｍ^ｍ＋はオニウム陽イオンを表し、ｍは１〜３の整数であり、ｐは１〜８の整数である。）
４．上記式（２）に示す構造単位において、上記Ａが−（ＣＯ）Ｏ−Ａ’−であり、Ａ’が２価の炭化水素基、少なくとも１個以上のヘテロ原子を含む２価の炭化水素基又は単結合である、上記３に記載のネガ型感放射線性組成物。
５．上記式（２）に示す構造単位において、上記Ｒ^２がフッ素原子又は炭素数１〜１０の直鎖状若しくは分岐状のアルキル基である、上記３又は４に記載のネガ型感放射線性組成物。
６．上記ポリシロキサン［Ａ］が、下記一般式（３）で表される加水分解性シラン化合物、及び、下記一般式（４）で表される加水分解性シラン化合物から選ばれる少なくとも１種を加水分解縮合させて得られた重合体である、上記１〜５のいずれか１項に記載のネガ型感放射線性組成物。
Ｒ^３ _ａＳｉ（ＯＲ^４）_４−ａ （３）
（式中、Ｒ^３は水素原子、フッ素原子、炭素数１〜５の直鎖状若しくは分岐状のアルキル基、シアノ基、シアノアルキル基又はアルキルカルボニルオキシ基を表し、Ｒ^４は１価の有機基を表し、ａは１〜３の整数を示す。）
Ｓｉ（ＯＲ^５）_４ （４）
（式中、Ｒ^５は１価の有機基を示す。）
７．上記ポリシロキサン［Ａ］を１００重量部に対して、上記重合体［Ｂ］の含有量が１〜３０重量部である上記１〜６のいずれか１項に記載のネガ型感放射線性組成物。
８．上記１〜７のいずれか１項に記載のネガ型感放射線性組成物を基板に塗布し、塗膜を形成する工程（ｉ）と、上記工程（ｉ）により得られた塗膜をベークする工程（ｉｉ）と、上記工程（ｉｉ）により得られた膜を露光する工程（ｉｉｉ）と、上記工程（ｉｉｉ）により得られた、露光された膜をベークする工程（ｉｖ）と、上記工程（ｉｖ）により得られた膜を現像液で現像し、ネガ型パターンを形成する工程（ｖ）と、上記工程（ｖ）により得られたネガ型パターンに、高エネルギー線照射及び加熱のうちの少なくとも一方の硬化処理を施し、硬化パターンを形成する工程（ｖｉ）と、を備えることを特徴とする硬化パターン形成方法。
８．上記７に記載の硬化パターン形成方法によって得られたことを特徴とする硬化パターン。 The present invention is as follows.
1. [A] a polysiloxane having a silanol group, [B] a polymer having a structural unit represented by the following general formula (1), and having a weight average molecular weight of 1,000 to 100,000, and [C] A negative-type radiation-sensitive composition comprising a solvent.

(In the formula, R ¹ represents a hydrogen atom, a methyl group, or a trifluoromethyl group, and Z represents a group that generates an acid by radiation.)
2. 2. The negative radiation-sensitive composition according to 1 above, wherein Z is a group that becomes an anion by radiation in the polymer having the structural unit represented by the general formula (1).
3. The negative radiation-sensitive composition according to 1 or 2, wherein the structural unit represented by the general formula (1) is a structural unit represented by the following general formula (2).

(In the formula, R ¹ represents a hydrogen atom, a methyl group or a trifluoromethyl group, and each R ² independently represents a hydrogen atom, a substituted or unsubstituted C 1-10 linear or branched group. Represents an alkyl group, a fluorine atom or a linear or branched perfluoroalkyl group having 1 to 10 carbon atoms, A represents a single bond or a divalent organic group, and G represents a single bond or a divalent group containing a fluorine atom. M ^{m +} represents an onium cation, m is an integer of 1 to 3, and p is an integer of 1 to 8.)
4). In the structural unit represented by the formula (2), A is — (CO) OA′—, A ′ is a divalent hydrocarbon group, and a divalent hydrocarbon containing at least one heteroatom. The negative radiation-sensitive composition according to the above 3, which is a group or a single bond.
5). The negative radiation-sensitive composition according to 3 or 4 above, wherein in the structural unit represented by the formula (2), R ² is a fluorine atom or a linear or branched alkyl group having 1 to 10 carbon atoms. .
6). The polysiloxane [A] hydrolyzes at least one selected from the hydrolyzable silane compound represented by the following general formula (3) and the hydrolyzable silane compound represented by the following general formula (4). 6. The negative radiation sensitive composition according to any one of 1 to 5 above, which is a polymer obtained by condensation.
R ³ _a Si (OR ⁴ ) _4-a (3)
(Wherein R ³ represents a hydrogen atom, a fluorine atom, a linear or branched alkyl group having 1 to 5 carbon atoms, a cyano group, a cyanoalkyl group, or an alkylcarbonyloxy group, and R ⁴ represents a monovalent organic group. Represents a group, and a represents an integer of 1 to 3.)
Si (OR ⁵ ) ₄ (4)
(In the formula, R ⁵ represents a monovalent organic group.)
7). The negative radiation-sensitive composition according to any one of 1 to 6 above, wherein the content of the polymer [B] is 1 to 30 parts by weight with respect to 100 parts by weight of the polysiloxane [A]. .
8). The negative radiation-sensitive composition according to any one of 1 to 7 above is applied to a substrate, and a step (i) for forming a coating film and a coating film obtained by the step (i) are baked. Step (ii), step (iii) of exposing the film obtained by the above step (ii), step (iv) of baking the exposed film obtained by the above step (iii), and the above step The step (v) of developing the film obtained in (iv) with a developer to form a negative pattern, and the negative pattern obtained in the step (v) are subjected to high energy beam irradiation and heating. And a step (vi) of performing at least one curing treatment to form a cured pattern.
8). 8. A cured pattern obtained by the cured pattern forming method according to 7 above.

  Since the negative radiation sensitive composition of the present invention is excellent in resolution, fine patterning is possible and a cured pattern having a low relative dielectric constant can be easily formed. Therefore, it can be used not only as a material for fine processing of semiconductor elements such as LSI, system LSI, DRAM, SDRAM, RDRAM, and D-RDRAM, but also as an interlayer insulating film material, particularly including a copper damascene process. Useful for semiconductor devices. Further, the cured pattern forming method of the present invention can be suitably used in a processing process that requires an interlayer insulating film having a low relative dielectric constant material, and greatly improves the efficiency of the processing process using a conventional interlayer insulating film. Can be improved.

Hereinafter, the present invention will be described in detail.
1. Negative-type radiation-sensitive composition The negative-type radiation-sensitive composition of the present invention is represented by [A] polysiloxane (hereinafter referred to as “polysiloxane [A]”), [B] represented by the following general formula (1). And a polymer having a weight average molecular weight of 1,000 to 100,000 (hereinafter simply referred to as “polymer [B]”) and a [C] solvent (hereinafter referred to as “solvent [C]”). ) ". ).

1-1. Polysiloxane [A]
The polysiloxane [A] includes an organosilicon compound represented by the following general formula (3) (hereinafter also referred to as “compound (A1)”) and an organosilicon compound represented by the following general formula (4) ( Hereinafter, the hydrolyzable silane is obtained by hydrolytic condensation of at least one hydrolyzable silane compound selected from “compound (A2)”, and preferably contains the compound (A1). It is obtained by hydrolytic condensation of a compound.

^{_{R 3 a Si (OR 4)}} 4-a (3)
(Wherein R ³ represents a hydrogen atom, a fluorine atom, a linear or branched alkyl group having 1 to 5 carbon atoms, a cyano group, a cyanoalkyl group, or an alkylcarbonyloxy group, and R ⁴ represents a monovalent organic group. Represents a group, and a represents an integer of 1 to 3.)

Si (OR ⁵ ) ₄ (4)
(In the formula, R ⁵ represents a monovalent organic group.)

1-1-1. Compound (A1)
Examples of the linear or branched alkyl group having 1 to 5 carbon atoms in R ³ of the general formula (3) include a methyl group, an ethyl group, a propyl group, a butyl group, a vinyl group, a propenyl group, and a 3-butenyl group. , 3-pentenyl group, 3-hexenyl group and the like. In addition, one or two or more hydrogen atoms in these alkyl groups may be substituted with a fluorine atom or the like.
In addition, examples of the cyanoalkyl group in R ³ include a cyanoethyl group and a cyanopropyl group.
Furthermore, examples of the alkylcarbonyloxy group in R ³ include a methylcarbonyloxy group, an ethylcarbonyloxy group, a propylcarbonyloxy group, a butylcarbonyloxy group, a vinylcarbonyloxy group, and an allylcarbonyloxy group.
When a plurality of R ³ are present (that is, when a is 2 or 3), all R ³ may be the same, or all or part of them may be different.

Examples of the monovalent organic group for R ⁴ include an alkyl group, an alkenyl group, an aryl group, an allyl group, and a glycidyl group. Among these, an alkyl group and an aryl group are preferable.
As said alkyl group, a C1-C5 linear or branched alkyl group is mentioned. Specific examples include a methyl group, an ethyl group, a propyl group, and a butyl group. In addition, one or two or more hydrogen atoms in these alkyl groups may be substituted with a fluorine atom or the like.
Examples of the aryl group include a phenyl group, a naphthyl group, a methylphenyl group, an ethylphenyl group, a chlorophenyl group, a bromophenyl group, and a fluorophenyl group. Among these, a phenyl group is preferable.
Examples of the alkenyl group include a vinyl group, a propenyl group, a 3-butenyl group, a 3-pentenyl group, and a 3-hexenyl group.

  Specific examples of the compound (A1) represented by the general formula (3) include methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltriisopropoxysilane, methyltri-n-butoxysilane, Methyltri-sec-butoxysilane, methyltri-tert-butoxysilane, methyltriphenoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-n-propoxysilane, ethyltriisopropoxysilane, ethyltri-n-butoxysilane, ethyltri -Sec-butoxysilane, ethyltri-tert-butoxysilane, ethyltriphenoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltri-n-propoxysilane, -Propyltriisopropoxysilane, n-propyltri-n-butoxysilane, n-propyltri-sec-butoxysilane, n-propyltri-tert-butoxysilane, n-propyltriphenoxysilane, isopropyltrimethoxysilane, isopropyl Triethoxysilane, isopropyltri-n-propoxysilane, isopropyltriisopropoxysilane, isopropyltri-n-butoxysilane, isopropyltri-sec-butoxysilane, isopropyltri-tert-butoxysilane, isopropyltriphenoxysilane, n-butyl Trimethoxysilane, n-butyltriethoxysilane, n-butyltri-n-propoxysilane, n-butyltriisopropoxysilane, n-butyltri-n-butoxysilane, - butyltri -sec- butoxysilane, n- butyltri -tert- butoxysilane, n- butyl triphenoxy silane,

  sec-butyltrimethoxysilane, sec-butylisotriethoxysilane, sec-butyltri-n-propoxysilane, sec-butyltriisopropoxysilane, sec-butyltri-n-butoxysilane, sec-butyltri-sec-butoxysilane, sec-butyltri-tert-butoxysilane, sec-butyltriphenoxysilane, tert-butyltrimethoxysilane, tert-butyltriethoxysilane, tert-butyltri-n-propoxysilane, tert-butyltriisopropoxysilane, tert-butyltri -N-butoxysilane, tert-butyltri-sec-butoxysilane, tert-butyltri-tert-butoxysilane, tert-butyltriphenoxysilane, dimethyldimeth Sisilane, dimethyldiethoxysilane, dimethyldi-n-propoxysilane, dimethyldiisopropoxysilane, dimethyldi-n-butoxysilane, dimethyldi-sec-butoxysilane, dimethyldi-tert-butoxysilane, dimethyldiphenoxysilane, diethyldimethoxysilane, Diethyldiethoxysilane, diethyldi-n-propoxysilane, diethyldiisopropoxysilane, diethyldi-n-butoxysilane, diethyldi-sec-butoxysilane, diethyldi-tert-butoxysilane, diethyldiphenoxysilane, di-n-propyldimethoxy Silane, di-n-propyldiethoxysilane, di-n-propyldi-n-propoxysilane, di-n-propyldiisopropoxysilane, di-n-propyldi-n-butyl Kishishiran, di -n- propyl di -sec- butoxysilane, di -n- propyl di -tert- butoxysilane, di -n- propyl di - phenoxy silane,

  Diisopropyldimethoxysilane, diisopropyldiethoxysilane, diisopropyldi-n-propoxysilane, diisopropyldiisopropoxysilane, diisopropyldi-n-butoxysilane, diisopropyldi-sec-butoxysilane, diisopropyldi-tert-butoxysilane, diisopropyldiphenoxy Silane, di-n-butyldimethoxysilane, di-n-butyldiethoxysilane, di-n-butyldi-n-propoxysilane, di-n-butyldiisopropoxysilane, di-n-butyldi-n-butoxysilane , Di-n-butyldi-sec-butoxysilane, di-n-butyldi-tert-butoxysilane, di-n-butyldi-phenoxysilane, di-sec-butyldimethoxysilane, di-sec-butyldiethoxy Lan, di-sec-butyldi-n-propoxysilane, di-sec-butyldiisopropoxysilane, di-sec-butyldi-n-butoxysilane, di-sec-butyldi-sec-butoxysilane, di-sec-butyldi -Tert-butoxysilane, di-sec-butyldi-phenoxysilane, di-tert-butyldimethoxysilane, di-tert-butyldiethoxysilane, di-tert-butyldi-n-propoxysilane, di-tert-butyldiiso Examples include propoxysilane, di-tert-butyldi-n-butoxysilane, di-tert-butyldi-sec-butoxysilane, di-tert-butyldi-tert-butoxysilane, and di-tert-butyldi-phenoxysilane.

Among these, as the compound (A1), methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-isopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, dimethyldimethoxysilane, dimethyl Diethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane and the like are preferable.
In addition, these compounds (A1) may be used individually by 1 type, and may be used in combination of 2 or more type.

1-1-2. Compound (A2)
As the monovalent organic group in R ⁵ of the general formula (4), the description of the monovalent organic group in R ⁴ of the general formula (3) can be applied as it is.

Examples of the compound (A2) represented by the general formula (4) include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-isopropoxysilane, tetra-n-butoxysilane, and tetra-sec-butoxysilane. , Tetra-tert-butoxysilane, tetraphenoxysilane and the like.
Among these, tetramethoxysilane and tetraethoxysilane are preferable.
In addition, these compounds (A2) may be used individually by 1 type, and may be used in combination of 2 or more type.

1-1-3. Other compounds As the hydrolyzable silane compound for obtaining the polysiloxane [A], it is preferable to use only a hydrolyzable silane compound selected from the compounds (A1) and (A2). In addition to the compounds (A1) and (A2), a hydrolyzable silane compound represented by the following general formula (5) (hereinafter also referred to as “other compound (A3)”) may be used in combination.
^{_{R 6 x (R 7 O)}} 3-x Si- (R 10) z -Si (OR 8) 3-y R 9 y (5)
(Wherein R ^{6 to} R ⁹ are the same or different and represent a monovalent organic group, and R ¹⁰ represents an oxygen atom, a phenylene group or a group represented by — (CH ₂ ) _n — (where n Is an integer of 1 to 6, and x and y are the same or different, and are an integer of 0 to 2, and z is 0 or 1.)

As the monovalent organic group in R ^{6 to} R ⁹ of the general formula (5), a monovalent organic group in R ⁴ of the general formula (3) can be applied.

  In the above general formula (5), the compounds in the case where z = 0 are 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- Ethyldisilane, 1,1,1,2,2-pentaethoxy-2-ethyldisilane, 1,1,1,2,2-pentaphenoxy-2-ethyldisilane, 1,1,1,2,2-penta Methoxy-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-1,2,2-trimethyl Disilane, 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 1,2-diphenyldisilane, 1,2-dimethoxy-1,1,2,2-tetramethyldisilane, 1,2-diethoxy-1,1,2,2-tetramethyldisilane, 1,2-dipheno 1,1,2,2-tetramethyldisilane, 1,2-dimethoxy-1,1,2,2-tetraethyldisilane, 1,2-diethoxy-1,1,2,2-tetraethyldisilane, 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 and the like.

  Among these, as a compound in the case where z = 0 in the general formula (5), hexamethoxydisilane, hexaethoxydisilane, 1,1,2,2-tetramethoxy-1,2-dimethyldisilane, 1, 1,2,2-tetraethoxy-1,2-dimethyldisilane, 1,1,2,2-tetramethoxy-1,2-diphenyldisilane, 1,2-dimethoxy-1,1,2,2-tetramethyl Disilane, 1,2-diethoxy-1,1,2,2-tetramethyldisilane, 1,2-dimethoxy-1,1,2,2-tetraphenyldisilane, 1,2-diethoxy-1,1,2, 2-tetraphenyldisilane and the like are preferable.

  Furthermore, in the above general formula (5), the compounds in the case of z = 1 include bis (trimethoxysilyl) methane, bis (triethoxysilyl) methane, bis (tri-n-propoxysilyl) methane, bis ( Tri-isopropoxysilyl) 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-isopropoxysilyl) ethane, 1,2-bis ( Tri-n-butoxysilyl) ethane, 1,2-bis (tri-sec-butoxysilyl) ethane, 1,2-bis (tri-tert-but) Sisilyl) ethane, 1- (dimethoxymethylsilyl) -1- (trimethoxysilyl) methane, 1- (diethoxymethylsilyl) -1- (triethoxysilyl) methane, 1- (di-n-propoxymethylsilyl) -1- (tri-n-propoxysilyl) methane, 1- (di-isopropoxymethylsilyl) -1- (tri-isopropoxysilyl) methane, 1- (di-n-butoxymethylsilyl) -1- ( Tri-n-butoxysilyl) methane, 1- (di-sec-butoxymethylsilyl) -1- (tri-sec-butoxysilyl) methane, 1- (di-tert-butoxymethylsilyl) -1- (tri- tert-butoxysilyl) methane, 1- (dimethoxymethylsilyl) -2- (trimethoxysilyl) ethane, 1- (diethoxymethylsilyl) 2- (triethoxysilyl) ethane, 1- (di-n-propoxymethylsilyl) -2- (tri-n-propoxysilyl) ethane, 1- (di-isopropoxymethylsilyl) -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-isopropoxymethylsilyl) 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-isopropoxymethylsilyl) ethane, 1,2-bis (di-n-butoxymethylsilyl) ethane, 1, 2-bis (di-sec-butoxymethylsilyl) ethane, 1,2-bis (di-tert-butoxymethylsilyl) 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-isopropoxysilyl) ) Benzene, 1,3-bis (tri-n-butoxysilyl) benzene, 1,3-bis (tri-sec-butoxysilyl) benzene, 1,3- (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-isopropoxysilyl) benzene, 1,4-bis (tri-n-butoxysilyl) benzene, 1,4-bis (tri-sec-butoxysilyl) benzene, 1,4-bis ( And tri-tert-butoxysilyl) benzene.

Among these, in the above general formula (5), the compounds in the case of z = 0 include bis (trimethoxysilyl) methane, bis (triethoxysilyl) methane, and 1,2-bis (trimethoxysilyl) ethane. 1,2-bis (triethoxysilyl) ethane, 1- (dimethoxymethylsilyl) -1- (trimethoxysilyl) methane, 1- (diethoxymethylsilyl) -1- (triethoxysilyl) methane, 1- (Dimethoxymethylsilyl) -2- (trimethoxysilyl) ethane, 1- (diethoxymethylsilyl) -2- (triethoxysilyl) ethane, bis (dimethoxymethylsilyl) methane, bis (diethoxymethylsilyl) methane, 1,2-bis (dimethoxymethylsilyl) ethane, 1,2-bis (diethoxymethylsilyl) ethane, 1,2- (Trimethoxysilyl) benzene, 1,2-bis (triethoxysilyl) benzene, 1,3-bis (trimethoxysilyl) benzene, 1,3-bis (triethoxysilyl) benzene, 1,4-bis ( Trimethoxysilyl) benzene, 1,4-bis (triethoxysilyl) benzene and the like are preferable.
The compound (A3) represented by the general formula (5) may be used alone or in combination of two or more.

1-1-4. Properties of polysiloxane [A] The content ratio of the structural unit derived from the compound (A1) in the polysiloxane [A] is 100 mol% in the total of all structural units contained in the polysiloxane [A]. Preferably, it is 30-100 mol%, More preferably, it is 60-100 mol%, More preferably, it is 70-100 mol%. When this content ratio is 30 to 100 mol%, the balance between the process margin during the curing process and the film physical properties of the cured film becomes good.
Further, the content ratio of the structural unit derived from the compound (A2) is preferably 0 to 70 mol% when the total of all the structural units contained in the polysiloxane [A] is 100 mol%, and more Preferably it is 0-40 mol%, More preferably, it is 0-30 mol%. When the content ratio is 0 to 70 mol%, the balance between the process margin during the curing process and the film physical properties of the cured film becomes good.
Furthermore, the total of the structural unit derived from the compound (A1) and the structural unit derived from the compound (A2) is preferably 100 when the total of all the structural units contained in the polysiloxane [A] is 100 mol%. It is less than mol%, More preferably, it is 30-100 mol%, More preferably, it is 60-100 mol%. When the total content is 30 to 100 mol%, the effect of the structural unit derived from the compound (A1) and the structural unit derived from the compound (A2) in the polysiloxane [A] for pattern formation is Obtainable.

  Moreover, when the said polysiloxane [A] contains the structural unit derived from the said compound (A3), the content rate is when the sum total of all the structural units which comprise polysiloxane [A] is 100 mol%. The amount is preferably 50 mol% or less, more preferably 0 to 40 mol%, still more preferably 0 to 30 mol%. When this content is 50 mol% or less, the effects of the structural unit derived from the compound (A1) and the structural unit derived from the compound (A2) in the polysiloxane [A] for pattern formation are greatly inhibited. Without effect, the effect of the structural unit derived from the compound (A3) on the pattern formation can be obtained.

The content of carbon atoms in the polysiloxane [A] is preferably 8 to 40 atom%, more preferably 8 to 8% when the total number of atoms constituting the polysiloxane [A] is 100 atom%. 20 atomic percent. When this content is less than 8 atomic%, when a silica-based film is formed using a radiation-sensitive composition containing polysiloxane [A], it is difficult to obtain a film having a sufficiently low relative dielectric constant. On the other hand, when it exceeds 40 atomic%, the film shrinkage (pattern shrinkage) after the curing treatment is large, and a desired pattern is hardly obtained.
The content (atomic%) of the carbon atom of the polysiloxane [A] is determined by completely hydrolyzing the hydrolyzable group of the component (hydrolyzable silane compound) used for the synthesis of the polysiloxane [A]. It is obtained from the elemental composition when the generated silanol group is completely condensed to form a siloxane bond, and is specifically obtained from the following formula.
Carbon atom content (atomic%) = (number of carbon atoms in organic silica sol) / (total number of atoms in organic silica sol) × 100

  The polysiloxane [A] has a weight average molecular weight (hereinafter also referred to as “Mw”) of preferably 1,000 to 200,000, more preferably 5,000 to 150,000. When this Mw exceeds 200,000, gelation tends to occur. On the other hand, if it is less than 1,000, problems are likely to occur in coating properties and storage stability. The above Mw is a polystyrene conversion value measured by gel permeation chromatography (GPC).

1-1-5. Production method of polysiloxane [A] The polysiloxane [A] is prepared by dissolving a hydrolyzable silane compound, that is, the compounds (A1) to (A3) as a starting material, in an organic solvent. It can be produced by adding water intermittently or continuously to the solution to cause a hydrolysis condensation reaction. At this time, a catalyst may be used. This catalyst may be dissolved or dispersed in advance in an organic solvent, or may be dissolved or dispersed in the water to be added. Moreover, the temperature for performing a hydrolysis-condensation reaction is 0 degreeC-100 degreeC normally.

The starting material preferably contains the compound (A1) as described above. For example, when the polysiloxane [A] is produced using the compounds (A1) and (A2), the compound (A1) The reaction ratio (molar ratio) of the compound (A2), that is, the ratio of the compound (A1) / compound (A2) is preferably 3/7 to 10/0, more preferably 5/5 to 9/1. It is. A reaction ratio of 3/7 to 10/0 is preferable because polysiloxane [A] having good solubility in an alkali developer and appropriate substrate adhesion can be obtained.
In addition, when the said starting material contains a compound (A3), the usage-amount is from a viewpoint of storage stability, Preferably it is 1-50 mol with respect to 100 mol of compounds (A1), More preferably, it is 1-30 mol. It is.

  Although it does not specifically limit as water for performing the said hydrolysis-condensation reaction, It is preferable to use ion-exchange water. Moreover, the said water is used in the quantity used as 0.25-3 mol with respect to 1 mol of alkoxyl groups of the hydrolysable silane compound used, Preferably it is 0.3-2.5 mol. By using water in an amount in the above range, there is no possibility that the uniformity of the formed coating film will be lowered, and there is little possibility that the storage stability of the composition will be lowered.

  The organic solvent is not particularly limited, and examples thereof include propylene glycol monoethyl ether, propylene glycol monomethyl ether, and propylene glycol monopropyl ether.

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

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 can be 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, gallic 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, benzenesulfonic acid Monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, tartaric 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, diazabicyclononane. , Diazabicycloundecene, tetramethylammonium hydroxide and the like.
Examples of the inorganic base include ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide and the like.

As said catalyst, a metal chelate compound, an organic acid, and an inorganic acid are preferable. The said catalyst may be used independently and may be used in combination of 2 or more type.
Moreover, the usage-amount of the said catalyst is 0.001-10 mass parts normally with respect to 100 mass parts of said hydrolysable silane compounds, Preferably it is 0.01-10 mass parts.

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. Thereby, since the purity of the organic solvent is increased, a composition having excellent coating properties and excellent 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, and the reaction by-product has a boiling point lower than that of the organic solvent. , It can be distilled off under reduced pressure.

  In addition, the polysiloxane [A] in the present invention may be used after being isolated from the polymer solution, or may be used as it is. In addition, when using as a polymer solution, the solvent substituted by the below-mentioned solvent [C] may be used as needed.

  In the negative radiation sensitive composition of the present invention, the polysiloxane [A] may be included singly or in combination of two or more.

（式中、Ｒ^１は水素原子、メチル基又はトリフルオロメチル基を表し、Ｚは放射線により酸を発生する基を表す。） 1-2. Polymer [B]
This polymer [B] is a polymer having a structural unit represented by the following general formula (1) and having a weight average molecular weight (Mw) of 1,000 to 100,000. That is, if it has a structural unit represented by the following general formula (1) and Mw is 1,000 to 100,000, a polymer containing other structural units can be used.

(In the formula, R ¹ represents a hydrogen atom, a methyl group, or a trifluoromethyl group, and Z represents a group that generates an acid by radiation.)

（式中、Ｒ^２は、それぞれ、独立に、水素原子、置換若しくは非置換の炭素数１〜１０の直鎖状あるいは分岐状のアルキル基、フッ素原子又は炭素数１〜１０の直鎖状若しくは分岐状のパーフルオロアルキル基を表し、Ｍ^ｍ＋はオニウム陽イオンを表し、ｍは１〜３の整数である。）
尚、本明細書において、「放射線により酸を発生する」とは、その基が放射線を直接吸収することで生成した励起状態からの分解反応により酸を発生すること、及び、別の基が放射線を吸収することによって誘起された電子移動、エネルギー移動、励起錯体形成からの分解反応により酸を発生することを意味する。 In the general formula (1), Z is a group that generates an acid such as sulfonic acid by radiation, and can be an atomic group including the following formula (a). The atomic group containing the following formula (a) is a group that generates an acid by radiation and becomes an anion.

(In the formula, each R ² independently represents a hydrogen atom, a substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms, a fluorine atom, or a linear or branched group having 1 to 10 carbon atoms. Represents a branched perfluoroalkyl group, M ^{m +} represents an onium cation, and m is an integer of 1 to 3)
In this specification, “acid is generated by radiation” means that an acid is generated by a decomposition reaction from an excited state generated when the group directly absorbs radiation, and another group generates radiation. This means that an acid is generated by a decomposition reaction from electron transfer, energy transfer, and exciplex formation induced by absorption of.

In the above formula, R ² represents a hydrogen atom, a substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms, a fluorine atom, or a linear or branched perfluoro group having 1 to 10 carbon atoms. Represents an alkyl group. Two R ² may be the same or different.
Examples of the substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, Examples include linear alkyl groups such as decyl group; branched alkyl groups such as 2-propyl group, 2-butyl group, and tert-butyl group.
Examples of the linear or branched perfluoroalkyl group having 1 to 10 carbon atoms include trifluoromethyl group, pentafluoroethyl group, heptafluoropropyl group, nonafluorobutyl group, undecafluoropentyl group, and tridecafluorohexyl. Linear perfluoroalkyl group such as a group, pentadecafluoroheptyl group, heptadecafluorooctyl group, nonadecafluorononyl group, heneicosadecyl group; (1-trifluoromethyl) tetrafluoroethyl group, (1- Examples thereof include branched perfluoroalkyl groups such as (trifluoromethyl) hexafluoropropyl group and 1,1-bistrifluoromethyl-2,2,2-trifluoroethyl group.
In the present invention, from the viewpoint of resolution, R ² is preferably a fluorine atom or a trifluoromethyl group.

（式中、Ｒ^１は水素原子、メチル基又はトリフルオロメチル基を表し、Ｒ^２は、それぞれ、独立に、水素原子、置換若しくは非置換の炭素数１〜１０の直鎖状あるいは分岐状のアルキル基、フッ素原子又は炭素数１〜１０の直鎖状若しくは分岐状のパーフルオロアルキル基を表し、Ａは単結合又は２価の有機基を表し、Ｇは単結合又はフッ素原子を含む２価の有機基を表し、Ｍ^ｍ＋はオニウム陽イオンを表し、ｍは１〜３の整数であり、ｐは１〜８の整数である。） In the polymer [B] according to the present invention, the structural unit represented by the general formula (1) is preferably a structural unit represented by the following general formula (2).

(In the formula, R ¹ represents a hydrogen atom, a methyl group or a trifluoromethyl group, and each R ² independently represents a hydrogen atom, a substituted or unsubstituted C 1-10 linear or branched group. Represents an alkyl group, a fluorine atom or a linear or branched perfluoroalkyl group having 1 to 10 carbon atoms, A represents a single bond or a divalent organic group, and G represents a single bond or a divalent group containing a fluorine atom. M ^{m +} represents an onium cation, m is an integer of 1 to 3, and p is an integer of 1 to 8.)

In the general formula (2), A represents a single bond or a divalent organic group. The divalent organic group is preferably a divalent hydrocarbon group, —O— group, — (CO) O— group, —O (CO) — group, —CO— group, amide group, —SO ₂ —. Group,-(CO) OA'- group and the like.
Of the divalent hydrocarbon groups, a chain or cyclic hydrocarbon group is preferred. Specific examples thereof include a methylene group, an ethylene group, a propylene group such as a 1,3-propylene group or a 1,2-propylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, an octamethylene group, Nonamethylene group, Decamemethylene group, Undecamethylene group, Dodecamethylene group, Tridecamethylene group, Tetradecamethylene group, Pentacamethylene group, Hexadecamethylene group, Heptadecamethylene group, Octadecamethylene group, Nonadecamethylene group, Insalene group, 1-methyl-1,3-propylene group, 2-methyl-1,3-propylene group, 2-methyl-1,2-propylene group, 1-methyl-1,4-butylene group, 2-methyl -1,4-butylene group, methylidene group, ethylidene group, propylidene group, or 2-propylidene Saturated chain hydrocarbon groups such as, cyclobutylene groups such as 1,3-cyclobutylene groups, cyclopentylene groups such as 1,3-cyclopentylene groups, cyclohexylene groups such as 1,4-cyclohexylene groups, A monocyclic hydrocarbon ring group such as a cycloalkylene group having 3 to 10 carbon atoms such as a cyclooctylene group such as a 1,5-cyclooctylene group, a 1,4-norbornylene group or a 2,5-norbornylene group; Bridged cyclic hydrocarbon ring groups such as 2 to 4 cyclic hydrocarbon ring groups having 4 to 30 carbon atoms such as norbornylene group, 1,5-adamantylene group, adamantylene group such as 2,6-adamantylene group, etc. Is mentioned.

Examples of A ′ in the — (CO) OA ′ group include a divalent hydrocarbon group, a divalent hydrocarbon group containing at least one hetero atom, and a single bond.
The divalent hydrocarbon group is preferably a chain or cyclic hydrocarbon group. Specific examples thereof include a methylene group, an ethylene group, a propylene group such as a 1,3-propylene group or a 1,2-propylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, an octamethylene group, Nonamethylene group, Decamemethylene group, Undecamethylene group, Dodecamethylene group, Tridecamethylene group, Tetradecamethylene group, Pentacamethylene group, Hexadecamethylene group, Heptadecamethylene group, Octadecamethylene group, Nonadecamethylene group, Insalene group, 1-methyl-1,3-propylene group, 2-methyl-1,3-propylene group, 2-methyl-1,2-propylene group, 1-methyl-1,4-butylene group, 2-methyl -1,4-butylene group, methylidene group, ethylidene group, propylidene group, or 2-propylidene Saturated chain hydrocarbon groups such as, cyclobutylene groups such as 1,3-cyclobutylene groups, cyclopentylene groups such as 1,3-cyclopentylene groups, cyclohexylene groups such as 1,4-cyclohexylene groups, A monocyclic hydrocarbon ring group such as a cycloalkylene group having 3 to 10 carbon atoms such as a cyclooctylene group such as a 1,5-cyclooctylene group, a 1,4-norbornylene group or a 2,5-norbornylene group; Bridged cyclic hydrocarbon ring groups such as 2 to 4 cyclic hydrocarbon ring groups having 4 to 30 carbon atoms such as norbornylene group, 1,5-adamantylene group, adamantylene group such as 2,6-adamantylene group, etc. Is mentioned.
Examples of the divalent hydrocarbon group containing at least one hetero atom include an alkyleneoxyalkylene group, an alkylenesulfonylalkylene group, an alkylenethioalkylene group, an alkyleneoxycarbonylalkylene group, and an alkylenecarbonylalkylene group.
A is preferably a — (CO) OA′— group, a single bond, a methylene group, an ethylene group, or a norbornylene group. Here, the single bond means a case where A does not exist in the general formula (2).
The above - include (CO) O-A'- _{group, - (CO) O-CH} 2 CH 2 CH 2 CH 2 - _{group, - (CO) O-CH} 2 CH 2 CH 2 - group, - (CO) An O—CH ₂ CH ₂ — group, — (CO) O—CH (CH ₃ ) — group, — (CO) O—CH ₂ CH ₂ —O—CH ₂ CH ₂ CH ₂ — group and the like are preferable.

In the general formula (2), G represents a divalent organic group containing a single bond or a fluorine atom. The divalent organic group containing a fluorine atom is preferably a hydrocarbon group in which part or all of the hydrogen atoms bonded to carbon of the divalent hydrocarbon group are substituted with fluorine atoms. The hydrocarbon group is preferably a chain or cyclic hydrocarbon group.
Preferred examples of G include a difluoromethylene group and a tetrafluoroethylene group.

  As a combination of A and G in the general formula (2), when G is a difluoromethylene group, A is preferably a — (CO) O— group, an ethylene group or a single bond, and G is a single bond. In this case, A is preferably a — (CO) O— group.

The above description is applied as it is to R ² in the general formula (2). Two R ² may be the same or different.

（式中、Ｒ^１２は、それぞれ、独立に、置換若しくは非置換の炭素数１〜１０のアルキル基、あるいは置換若しくは非置換の炭素数６〜１８のアリール基を表すか、又は、２つ以上のＲ^１２が相互に結合して式中の硫黄原子と共に環を形成している。）

（式中、Ｒ^１３は、それぞれ、独立に、置換若しくは非置換の炭素数１〜１０のアルキル基、あるいは置換若しくは非置換の炭素数６〜１８のアリール基を表すか、又は、２つのＲ^１３が相互に結合して式中のヨウ素原子と共に環を形成している。） In the general formula (2), M ^{m +} represents an onium cation. Examples of the onium cation include onium cations such as a sulfonium cation, an iodonium cation, a phosphonium cation, a diazonium cation, an ammonium cation, and a pyridinium cation.
Among these, a sulfonium cation represented by the following general formula (b) and an iodonium cation represented by the following general formula (c) are preferable.

(In the formula, each R ¹² independently represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 18 carbon atoms, or two or more thereof. R ¹² of each other is bonded to each other to form a ring together with the sulfur atom in the formula.)

(Wherein R ¹³ each independently represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 18 carbon atoms, or two R ¹³ are bonded to each other to form a ring together with the iodine atom in the formula.)

  In the general formulas (b) and (c), examples of the unsubstituted alkyl group having 1 to 10 carbon atoms include a linear or branched alkyl group, such as a methyl group, an ethyl group, an n-propyl group, Isopropyl group, n-butyl group, 1-methylpropyl group, 2-methylpropyl group, tert-butyl group, n-pentyl group, isopentyl group, 1,1-dimethylpropyl group, 1-methylbutyl group, n-hexyl group , Isohexyl group, 1,1-dimethylbutyl group, n-heptyl group, n-octyl group, isooctyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group and the like.

In addition, examples of the substituent of the substituted alkyl group include an aryl group having 6 to 30 carbon atoms, a linear, branched or cyclic alkenyl group having 2 to 30 carbon atoms, a halogen atom, an oxygen atom, and a nitrogen atom. , Groups having 1 to 30 atoms including heteroatoms such as sulfur atom, phosphorus atom and silicon atom.
Accordingly, in the above general formulas (b) and (c), the substituted linear or branched alkyl group having 1 to 10 carbon atoms includes benzyl group, methoxymethyl group, methylthiomethyl group, ethoxymethyl group, ethyl Thiomethyl, phenoxymethyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, acetylmethyl, fluoromethyl, trifluoromethyl, chloromethyl, trichloromethyl, 2-fluoropropyl, (trifluoroacetyl) Methyl group, (trichloroacetyl) methyl group, (pentafluorobenzoyl) methyl group, aminomethyl group, (cyclohexylamino) methyl group, (trimethylsilyl) methyl group, 2-phenylethyl group, 2-aminoethyl group, 3-phenylpropiyl And the like.

  In the general formulas (b) and (c), examples of the unsubstituted aryl group having 6 to 18 carbon atoms include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthryl group, and a 1-phenanthryl group. Can be mentioned. Examples of the substituent for these aryl groups include linear, branched or cyclic alkyl groups having 1 to 30 carbon atoms, and heteroatoms such as halogen atoms, oxygen atoms, nitrogen atoms, sulfur atoms, phosphorus atoms and silicon atoms. Examples thereof include a group having 1 to 30 atoms. Examples of the substituted aryl group having 6 to 18 carbon atoms include o-tolyl group, m-tolyl group, p-tolyl group, 4-hydroxyphenyl group, 4-methoxyphenyl group, mesityl group, o-cumenyl group, 2,3-xylyl group, 2,4-xylyl group, 2,5-xylyl group, 2,6-xylyl group, 3,4-xylyl group, 3,5-xylyl group, 4-fluorophenyl group, 4- A trifluoromethylphenyl group, 4-chlorophenyl group, 4-bromophenyl group, 4-iodophenyl group and the like can be mentioned.

In the general formula (b), examples of the ring formed by two or more R ¹² bonded to each other together with the sulfur atom in the formula include a 5- to 7-membered ring structure.
Moreover, in said general formula (c), as a ring which two R < ¹³ > couple | bonds together and forms with the iodine atom in a formula, 5-7 membered ring structure etc. are mentioned.

Preferred examples of the sulfonium cation and the iodonium cation represented by the general formulas (b) and (c) are shown below.

  Moreover, in the said General formula (2), p is an integer of 1-8, However, From a viewpoint of resolution, Preferably it is 1 or 2.

Preferred compounds giving the structural unit represented by the general formula (2) are shown below.

  The content of the structural unit represented by the general formula (1) contained in the polymer [B] is preferably when the total amount of the structural units constituting the polymer [B] is 100 mol%. Is 1-30 mol%, more preferably 1-15 mol%. If it is less than 1 mol%, the sensitivity and developability may decrease. On the other hand, if it exceeds 30 mol%, the transparency to radiation may be reduced, making it difficult to obtain a rectangular resist pattern.

（式中、Ｒ^１４は、水素原子、メチル基又はトリフルオロメチル基を表し、各Ｒ^１５は、それぞれ、独立に、炭素数４〜２０の１価の脂環式炭化水素基若しくはその誘導体、又は炭素数１〜４の直鎖状若しくは分岐状のアルキル基を表し、かつＲ^１５の少なくとも１つが該脂環式炭化水素基若しくはその誘導体であるか、あるいは何れか２つのＲ^１５が相互に結合して、それぞれが結合している炭素原子と共に炭素数４〜２０の２価の脂環式炭化水素基若しくはその誘導体を形成して、残りのＲ^１５が炭素数１〜４の直鎖状若しくは分岐状のアルキル基又は炭素数４〜２０の１価の脂環式炭化水素基若しくはその誘導体を表す。）

（式中、Ｒ^１７は、水素原子、メチル基又はトリフルオロメチル基を表し、ｔは０又は１である。） The polymer [B] may be a polymer composed of the structural unit represented by the general formula (1) and another structural unit as described above.
Examples of the monomer that gives another structural unit include a compound represented by the following general formula (6), a compound represented by the following general formula (7), an α-hydroxymethyl acrylate ester, an unsaturated nitrile compound, Monofunctional compounds such as saturated amide compounds, nitrogen-containing vinyl compounds, (meth) acryloyloxylactone compounds having acid-dissociable groups, (meth) acryloyloxylactone compounds having no acid-dissociable groups, bridged hydrocarbons (Meth) acrylic acid ester having a skeleton, carboxyl group-containing ester having a bridged hydrocarbon skeleton of unsaturated carboxylic acid, unsaturated carboxylic acid (anhydride), bridged hydrocarbon skeleton of unsaturated carboxylic acid Carboxyl group-containing esters, polyfunctional compounds having a bridged hydrocarbon skeleton, polyfunctional compounds having no bridged hydrocarbon skeleton, etc. It is.

(Wherein R ¹⁴ represents a hydrogen atom, a methyl group or a trifluoromethyl group, and each R ¹⁵ independently represents a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof, Or a linear or branched alkyl group having 1 to 4 carbon atoms and at least one of R ¹⁵ is the alicyclic hydrocarbon group or a derivative thereof, or any two R ¹⁵ are mutually To form a divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof together with the carbon atoms to which each is bonded, and the remaining R ¹⁵ is a straight chain having 1 to 4 carbon atoms. Alternatively, it represents a branched alkyl group, a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms, or a derivative thereof.)

(Wherein R ¹⁷ represents a hydrogen atom, a methyl group or a trifluoromethyl group, and t is 0 or 1).

In the compound represented by the general formula (6), a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms of R ¹⁵ and any two R ¹⁵ bonded to each other have 4 carbon atoms. As the divalent alicyclic hydrocarbon group of ˜20, fatty acids derived from norbornane, tricyclodecane, tetracyclododecane, adamantane, cycloalkanes such as cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, etc. A group consisting of an alicyclic ring; a group consisting of these alicyclic rings may be a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a 2-methylpropyl group, a 1-methylpropyl group, -The group etc. which substituted by 1 or more types or 1 or more of C1-C4 linear, branched or cyclic alkyl groups, such as a butyl group, can be mentioned. Among these alicyclic hydrocarbon groups, the group consisting of an alicyclic ring derived from norbornane, tricyclodecane, tetracyclododecane, adamantane, cyclopentane or cyclohexane, or a group consisting of these alicyclic rings is described above. A group substituted with an alkyl group is preferred.

  The alicyclic hydrocarbon group derivatives include hydroxyl group; carboxyl group; oxo group (that is, ═O group); hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl. A hydroxyalkyl group having 1 to 4 carbon atoms such as a group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group; Group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, 2-methylpropoxy group, 1-methylpropoxy group, tert-butoxy group and the like, alkoxy group having 1 to 4 carbon atoms; cyano group; cyanomethyl Group having 2 to 5 carbon atoms such as 2-cyanoethyl group, 3-cyanopropyl group, 4-cyanobutyl group, etc. A substituent such as Noarukiru group include one or more or one or more having groups. Of these substituents, a hydroxyl group, a carboxyl group, a hydroxymethyl group, a cyano group, a cyanomethyl group, and the like are preferable.

Examples of the linear or branched alkyl group having 1 to 4 carbon atoms of R ¹⁵ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a 2-methylpropyl group, 1- A methylpropyl group, a tert-butyl group, etc. can be mentioned. Of these alkyl groups, a methyl group and an ethyl group are preferable.

The -COOC (R ¹⁵ ) ₃ moiety in the general formula (6) is a moiety that is dissociated by the action of an acid to form a carboxyl group. The -COOC ^(R _{15) 3} ^-C in a portion ^(R _{15) 3} moiety, the following formula (6a), formula (6b), a group represented by the formula (6c) or Formula (6d).

In the above formula (6a), formula (6b) and formula (6c), each R ¹⁶ independently represents a linear or branched alkyl group having 1 to 4 carbon atoms, and m ′ is 0 or 1. is there.
Examples of the linear or branched alkyl group having 1 to 4 carbon atoms of R ¹⁶ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a 2-methylpropyl group, 1- Examples thereof include a methylpropyl group and a tert-butyl group. Of these alkyl groups, a methyl group and an ethyl group are preferred.
The group represented by the formula (6a), in particular, the two R ¹⁶ are both methyl groups groups. As the group represented by the above formula (6b), a group in which R ¹⁶ is a methyl group or an ethyl group is particularly preferable. The group represented by the above formula (6c) is particularly a group in which m ′ is 0 and R ¹⁶ is a methyl group, a group in which m ′ is 0 and R ¹⁶ is an ethyl group, and m ′ is 1. A group in which R ¹⁶ is a methyl group and a group in which m ′ is 1 and R ¹⁶ is an ethyl group are preferred.

Specific examples of Formula (6a), Formula (6b) and Formula (6c) are given below.

The (meth) acrylic acid ester having a bridged hydrocarbon skeleton includes norbornyl (meth) acrylate, isonorbornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, and tetracyclodecanyl (meth) acrylate. , (Meth) acrylic acid dicyclopentenyl, (meth) acrylic acid adamantyl, (meth) acrylic acid adamantylmethyl and the like.
Examples of the carboxyl group-containing ester having a bridged hydrocarbon skeleton of unsaturated carboxylic acid include carboxynorbornyl (meth) acrylate, carboxytricyclodecanyl (meth) acrylate, and carboxytetracyclodecane (meth) acrylate. Nil and the like.
Examples of (meth) acrylic acid esters having no bridged hydrocarbon skeleton include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and n-butyl (meth) acrylate. 2-methylpropyl (meth) acrylate, 1-methylpropyl (meth) acrylate, tert-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (Meth) acrylic acid 3-hydroxypropyl, (meth) acrylic acid cyclopropyl, (meth) acrylic acid cyclopentyl, (meth) acrylic acid cyclohexyl, (meth) acrylic acid 4-methoxycyclohexyl, (meth) acrylic acid 2-cyclopentyl Oxycarbonylethyl, 2-cyclohexyloxyca (meth) acrylic acid Boniruechiru include (meth) acrylic acid 2- (4-methoxy-cyclohexyl) oxycarbonyl ethyl and the like.
Examples of the unsaturated carboxylic acid (anhydride) include (meth) acrylic acid, crotonic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, and mesaconic acid. .
Examples of the carboxyl group-containing ester having no bridged hydrocarbon skeleton of unsaturated carboxylic acid include 2-carboxyethyl (meth) acrylate, 2-carboxypropyl (meth) acrylate, and 3-carboxy (meth) acrylate. And propyl, 4-carboxybutyl (meth) acrylate, 4-carboxycyclohexyl (meth) acrylate, and the like.
Examples of the polyfunctional compound having a bridged hydrocarbon skeleton include 1,2-adamantanediol di (meth) acrylate, 1,3-adamantanediol di (meth) acrylate, and 1,4-adamantanediol di (meta). ) Acrylate, tricyclodecanyl dimethylol di (meth) acrylate, and the like.

  In the polymer [B], for example, each of the above compounds may be prepared by using a radical polymerization initiator such as hydroperoxides, dialkyl peroxides, diacyl peroxides, azo compounds, etc. It can be produced by polymerization in the presence of a suitable solvent. 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; cyclohexane, cycloheptane, cyclooctane, decalin, norbornane, and the like. Cycloalkanes; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene; halogenated hydrocarbons such as chlorobutanes, bromohexanes, dichloroethanes, hexamethylene dibromide, chlorobenzene; ethyl acetate, acetic acid saturated carboxylic acid esters such as n-butyl, isobutyl acetate and methyl propionate; ketones such as 2-butanone, 4-methyl-2-pentanone and 2-heptanone; tetrahydrofuran, dimethoxyethanes, diethoxyethanes and the like AEs are listed. These solvents may be used alone or in combination of two or more. The reaction temperature in the polymerization is usually 40 ° C to 120 ° C, preferably 50 ° C to 90 ° C. The reaction time is usually 1 to 48 hours, preferably 1 to 24 hours.

  The polymer [B] has a weight average molecular weight of 1,000 to 100,000, preferably 1,500 to 80,000, more preferably 2,000 to 50,000. When Mw of the said polymer [B] is less than 1,000, the heat resistance of the cured film obtained using the negative radiation sensitive composition of this invention may not be enough. On the other hand, when Mw exceeds 100,000, the developability of the film obtained using the negative radiation-sensitive composition of the present invention may be lowered when forming a cured pattern. The above Mw is a polystyrene conversion value measured by gel permeation chromatography (GPC).

  In the negative radiation sensitive composition of the present invention, the polymer [B] may be included singly or in combination of two or more.

  The content of the polymer [B] contained in the negative radiation-sensitive composition of the present invention is preferably 1 to 40 parts by mass, more preferably 1 with respect to 100 parts by mass of the polysiloxane [A]. -30 mass parts, More preferably, it is 1-20 mass parts. If it is the said content, it can mix, maintaining favorable compatibility.

1-3. Solvent [C]
The solvent [C] is usually an organic solvent, such as an alcohol solvent, a ketone solvent, an amide solvent, an ether solvent, an ester solvent, an aliphatic hydrocarbon solvent, an aromatic solvent, or a halogen-containing solvent. Is mentioned.
In the negative radiation sensitive composition of the present invention, components such as polysiloxane [A] and polymer [B] are dissolved or dispersed in this solvent [C].

  Examples of the alcohol solvent include a monoalcohol solvent, a polyhydric alcohol solvent, a polyhydric alcohol partial ether solvent, and the like. These can be used alone or in combination of two or more.

  Monoalcohol solvents include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-pentanol, isopentanol, 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-heptadecyl Alcohol, furfuryl alcohol, phenol, cyclohexanol, methyl cyclohexanol, 3,3,5-trimethyl cyclohexanol, benzyl alcohol, diacetone alcohol and the like. These may be used alone or in combination of two or more.

  Examples of the polyhydric alcohol solvent include ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, Examples include 2,4-heptanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, and tripropylene glycol. These may be used alone or in combination of two or more.

  Polyhydric alcohol partial ether solvents include 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- Ethyl butyl 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 Over mono butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, and the like. These may be used alone or in combination of two or more.

  Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, diethyl ketone, methyl isobutyl ketone, methyl n-pentyl ketone, ethyl n-butyl ketone, and methyl n-hexyl ketone. , Diisobutyl ketone, trimethylnonanone, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, 2-hexanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, diacetone alcohol, acetophenone, fenchon, etc. Can be mentioned. These may be used alone or in combination of two or more.

  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. These may be used alone or in combination of two or more.

  Examples of the ether solvents include ethyl ether, isopropyl ether, n-butyl ether, n-hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2-propylene oxide, dioxolane, 4-methyldioxolane, dioxane, dimethyldioxane, ethylene glycol. Monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-n-hexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl ether, Ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene Recall dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol di-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxytriglycol, tetraethylene glycol di-n-butyl 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, tripropylene glycol monomethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, diphenyl Ether, anisole, and the like. These may be used alone or in combination of two or more.

  Examples of the ester solvent include diethyl carbonate, propylene carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, and acetic acid. n-pentyl, 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, methyl acetoacetate, acetoacetate Ethyl acetate, ethylene glycol monomethyl ether, acetate ethylene glycol monoethyl ether, acetate diethylene glycol monomethyl ether, acetate diethylene glycol monoethyl ether, acetate diethylene glycol 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, glycol diacetate, Methoxytriglycol acetate, ethyl propionate, n-butyl propionate, isoamyl 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. These may be used alone or in combination of two or more.

Examples of the aliphatic hydrocarbon solvent include n-pentane, isopentane, n-hexane, isohexane, n-heptane, isoheptane, 2,2,4-trimethylpentane, n-octane, isooctane, cyclohexane, and methylcyclohexane. It is done. These may be used alone or in combination of two or more.
Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propyl benzene, isopropyl benzene, diethyl benzene, isobutyl benzene, triethyl benzene, diisopropyl benzene, n-amyl naphthalene, and trimethyl benzene. Etc. These may be used alone or in combination of two or more.
Examples of the halogen-containing solvent include dichloromethane, chloroform, chlorofluorocarbon, chlorobenzene, dichlorobenzene and the like. These may be used alone or in combination of two or more.

As said solvent [C], when forming a hardening pattern using the negative radiation sensitive composition of this invention, after baking a coating film (PB), from a viewpoint of reducing the amount of residual solvent in a film | membrane, It is preferable to use an organic solvent having a boiling point of less than 150 ° C. In particular, it is preferable to use one or more of alcohol solvents, ketone solvents and ester solvents.
In addition, the said solvent [C] may be the same as the organic solvent used as a reaction solvent at the time of the synthesis | combination of polysiloxane [A]. Further, after the synthesis of polysiloxane [A] is completed, the solvent can be replaced with a desired organic solvent.

1-4. Additives The negative radiation-sensitive composition of the present invention may contain additives such as acid diffusion control agents and surfactants.

The above acid diffusion control agent controls the diffusion phenomenon in the resist film of the acid generated by the exposure of the dry film obtained using the negative radiation-sensitive composition of the present invention, such as ultraviolet rays, and is not preferable in the unexposed area. It is a component having an action of suppressing a chemical reaction.
By compounding such an acid diffusion control agent, the resolution as a resist is further improved, and the change in the line width of the resist pattern due to fluctuations in the holding time (PED) from exposure to development can be suppressed. Excellent process stability can be obtained.

  The acid diffusion controller is preferably a nitrogen-containing organic compound whose basicity does not change by exposure or heating.

  Examples of the nitrogen-containing organic compound include tertiary amine compounds, amide group-containing compounds, quaternary ammonium hydroxide compounds, and nitrogen-containing heterocyclic compounds. These may be used individually by 1 type and may be used in combination of 2 or more type.

  Examples of the tertiary amine compound include triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine. , Tri-n-nonylamine, tri-n-decylamine, cyclohexyldimethylamine, dicyclohexylmethylamine, tricyclohexylamine and the like tri (cyclo) alkylamines; aniline, N-methylaniline, N, N-dimethylaniline, 2- Aromatic amines such as methylaniline, 3-methylaniline, 4-methylaniline, 4-nitroaniline, 2,6-dimethylaniline, 2,6-diisopropylaniline, diphenylamine, triphenylamine, naphthylamine; triethanolamine, Gietano Alkanolamines such as ruaniline; N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetrakis (2-hydroxypropyl) ethylenediamine, 1,3-bis [1- (4 -Aminophenyl) -1-methylethyl] benzenetetramethylenediamine, 2,2-bis (4-aminophenyl) propane, 2- (3-aminophenyl) -2- (4-aminophenyl) propane, 2- ( 4-aminophenyl) -2- (3-hydroxyphenyl) propane, 2- (4-aminophenyl) -2- (4-hydroxyphenyl) propane, 1,4-bis [1- (4-aminophenyl)- 1-methylethyl] benzene, 1,3-bis [1- (4-aminophenyl) -1-methylethyl] benzene, bis (2-dimethylaminoethyl) ester Ether, bis (2-diethylaminoethyl) ether. These may be used alone or in combination of two or more.

  Examples of the amide group-containing compound include N-tert-butoxycarbonyldi-n-octylamine, N-tert-butoxycarbonyldi-n-nonylamine, N-tert-butoxycarbonyldi-n-decylamine, N-tert-butoxy. Carbonyldicyclohexylamine, N-tert-butoxycarbonyl-1-adamantylamine, N-tert-butoxycarbonyl-N-methyl-1-adamantylamine, N, N-di-tert-butoxycarbonyl-1-adamantylamine, N, N-di-tert-butoxycarbonyl-N-methyl-1-adamantylamine, N-tert-butoxycarbonyl-4,4′-diaminodiphenylmethane, N, N′-di-tert-butoxycarbonylhexamethylenediamine, N, N N ′, N′-tetra-tert-butoxycarbonylhexamethylenediamine, N, N-di-tert-butoxycarbonyl-1,7-diaminoheptane, N, N′-di-tert-butoxycarbonyl-1,8- Diaminooctane, N, N′-di-tert-butoxycarbonyl-1,9-diaminononane, N, N′-di-tert-butoxycarbonyl-1,10-diaminodecane, N, N′-di-tert-butoxy Carbonyl-1,12-diaminododecane, N, N′-di-tert-butoxycarbonyl-4,4′-diaminodiphenylmethane, N-tert-butoxycarbonylbenzimidazole, N-tert-butoxycarbonyl-2-methylbenzimidazole N-tert-butoxycarbonyl-2-phenylbenzene N-tert-butoxycarbonyl such as diimidazole, N-tert-butoxycarbonyl-pyrrolidine, N-tert-butoxycarbonyl-piperidine, N-tert-butoxycarbonyl-4-hydroxy-piperidine, N-tert-butoxycarbonyl-morpholine In addition to group-containing amino compounds, formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide, pyrrolidone, N-methylpyrrolidone and the like can be mentioned. . These may be used alone or in combination of two or more.

  Examples of the quaternary ammonium hydroxide compound include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-propylammonium hydroxide, and tetra-n-butylammonium hydroxide. These may be used alone or in combination of two or more.

  Examples of the nitrogen-containing heterocyclic compound include imidazoles such as imidazole, 4-methylimidazole, 1-benzyl-2-methylimidazole, 4-methyl-2-phenylimidazole, benzimidazole, and 2-phenylbenzimidazole; pyridine, 2 -Methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, 2-methyl-4-phenylpyridine, nicotine, nicotinic acid, nicotinamide, quinoline, 4 -Pyridines such as hydroxyquinoline, 8-oxyquinoline and acridine; piperazines such as piperazine and 1- (2-hydroxyethyl) piperazine, pyrazine, pyrazole, pyridazine, quinosaline, purine, pyrrolidine, piperidine, 3-piperidine Roh-1,2-propanediol, morpholine, 4-methylmorpholine, 1,4-dimethylpiperazine, 1,4-diazabicyclo [2.2.2] octane. These may be used alone or in combination of two or more.

  As the acid diffusion controller, a tertiary amine compound, an amide group-containing compound, and a nitrogen-containing heterocyclic compound are preferable because of its excellent content effect. Of these, the amide group-containing compound is preferably an N-tert-butoxycarbonyl group-containing amino compound, and the nitrogen-containing heterocyclic compound is preferably an imidazole.

  When the negative radiation-sensitive composition of the present invention contains an acid diffusion control agent, the content of the acid diffusion control agent is usually 15 parts by mass or less, preferably 100 parts by mass or less with respect to 100 parts by mass of the polysiloxane [A]. Is 10 parts by mass or less, more preferably 5 parts by mass or less. When this content exceeds 15 parts by mass, the sensitivity as a resist and the developability of the exposed part may be deteriorated. On the other hand, if the content is less than 0.001 part by mass, the fidelity of the pattern shape and dimensions as a resist may be lowered depending on the process conditions.

  The said surfactant is a component which has the effect | action which improves the applicability | paintability, striation, the developability after exposure, etc. of the negative radiation sensitive composition of this invention. As this surfactant, nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, silicone surfactants, polyalkylene oxide surfactants, fluorine surfactants, Examples include poly (meth) acrylate surfactants.

Nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene n-octylphenyl ether, polyoxyethylene n-nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol Examples include distearate.
In addition, as commercial products, “SH8400 FLUID” (manufactured by Toray Dow Corning Silicon Co.), “KP341” (manufactured by Shin-Etsu Chemical Co., Ltd.), “Polyflow No. 75”, “Polyflow No.” .95 "(above, manufactured by Kyoeisha Chemical Co., Ltd.)," F-top EF301 "," F-top EF303 "," F-top EF352 "(above, manufactured by Tochem Products)," Megafax F171 ",""MegafaxF173" (manufactured by Dainippon Ink & Chemicals, Inc.), "Florard FC430", "Florard FC431" (manufactured by Sumitomo 3M), "Asahi Guard AG710", "Surflon S-382""SurflonSC-101","SurflonSC-102","SurflonSC" 103 "," Surflon SC-104 "," Surflon SC-105 "," Surflon SC-106 "(manufactured by Asahi Glass Co., Ltd.).
As the surfactant, a fluorine-based surfactant and a silicone-based surfactant are preferable. In addition, these may be used individually by 1 type and may be used in combination of 2 or more type.
Moreover, when the negative radiation sensitive composition of this invention contains surfactant, content of surfactant is 0.00001-1 mass normally with respect to 100 mass parts of said polysiloxane [A]. Part.

1-5. Production method of negative radiation-sensitive composition The negative radiation-sensitive composition of the present invention is used as necessary in the polysiloxane [A], the polymer [B], and the solvent [C]. It can be obtained by mixing the additive with a known method.
In addition, the solid content concentration of the negative radiation composition of the present invention (concentration of all components except the solvent [C]) is appropriately selected according to the purpose, application, etc. %, And preferably 10 to 40% by mass. When the solid content concentration is 1 to 50% by mass, a film thickness of a coating film suitable for forming a cured pattern described later can be obtained.

2. Cured pattern and formation method thereof The cured pattern forming method of the present invention is obtained by applying the negative radiation sensitive composition of the present invention to a substrate to form a coating film (i) and the above step (i). A step (ii) of baking the obtained coating film, a step (iii) of exposing the film obtained by the step (ii), and a step of baking the exposed film obtained by the step (iii). (Iv) and developing the film obtained in the step (iv) with a developer to form a negative pattern, and the negative pattern obtained in the step (v) has high energy. And a step (vi) of performing a curing process of at least one of line irradiation and heating to form a cured pattern.

In the said process (i), a negative radiation sensitive composition is apply | coated to a board | substrate, and a coating film is formed.
Examples of the method for applying the composition include a spin coating method, a cast coating method, and a roll coating method. The coating conditions are selected in consideration of the coating method, the solid content concentration of the composition, the viscosity and the like so as to obtain a desired film thickness.
Examples of the substrate include a wafer coated with a Si-containing layer such as Si, SiO ₂ , SiN, SiC, or SiCN. In order to maximize the potential of the negative radiation sensitive composition, as disclosed in Japanese Patent Publication No. 6-12452 (Japanese Patent Laid-Open No. 59-93448), etc. It is also possible to form an organic or inorganic antireflection film.

The step (ii) is a step of baking the coating film (hereinafter referred to as “PB”), and the solvent in the coating film is volatilized by this step.
The PB heating condition is appropriately selected depending on the composition of the composition, but is preferably 60 ° C to 150 ° C, more preferably 70 ° C to 120 ° C.

  The step (iii) is a step of exposing the film (dry film) obtained in the step (ii). In this step, the surface of the film (dried film) is usually irradiated, that is, exposed to the radiation illustrated below through a photomask having a mask pattern for forming a desired pattern. As a result, the radiation passes through the opening of the photomask, further passes through the exposure lens, and reaches the film (dry coating). The exposed portion of the film (dry film) is removed by step (v).

  The exposure conditions in the step (iii) are appropriately selected depending on the composition (type of additive, etc.), thickness, etc. of the film (dry film). Examples of radiation used for this exposure include visible light rays, ultraviolet rays, far ultraviolet rays, X-rays, and charged particle beams such as electron beams. Among these, ArF excimer laser (wavelength 193 nm), KrF excimer laser, etc. Far ultraviolet rays and electron beams represented by (wavelength 248 nm) are preferable.

The step (iv) is a step of baking the exposed film (hereinafter referred to as “PEB”). By this step, the crosslinking reaction of the polymer contained in the exposed portion can be smoothly advanced.
The heating conditions for PEB are appropriately selected depending on the composition of the composition, but are preferably 30 ° C. to 200 ° C., more preferably 50 ° C. to 170 ° C., from the viewpoint of facilitating the crosslinking reaction.

The step (v) is a step of developing the film obtained in the step (iv) with a developer to form a negative pattern, and this step removes the unexposed portion in the step (iii). Then, a negative pattern reflecting the pattern of the exposed portion, that is, the opening of the photomask is left and formed.
As the developer, an alkaline aqueous solution obtained by dissolving an alkaline compound in water is usually used. Examples of the alkaline compound include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, 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] -5-nonene and the like. These may be used alone or in combination of two or more. Of the above compounds, tetramethylammonium hydroxide is particularly preferred. The concentration of the alkaline compound is usually 10% by mass or less. If this concentration is too high, the exposed area may also be dissolved in the developer.

The developer may be a solution containing only the alkaline compound or a composition containing an organic solvent, a surfactant and the like.
Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetonyl acetone, cyclopentanone, cyclohexanone, 3-methylcyclopentanone, and 2,6-dimethylcyclohexanone; methyl alcohol, ethyl alcohol, n- Alcohols such as propyl alcohol, isopropyl alcohol, n-butyl alcohol, tert-butyl alcohol, cyclopentanol, cyclohexanol, 1,4-hexanediol, 1,4-hexanedimethylol; ethers such as tetrahydrofuran and dioxane; Examples include esters such as ethyl acetate, n-butyl acetate and isoamyl acetate; aromatic hydrocarbons such as toluene and xylene; phenol and dimethylformamide. The said organic solvent may be used independently and may be used in combination of 2 or more.
When the developer contains an organic solvent, the content thereof is preferably 100 parts by volume or less with respect to 100 parts by volume of the alkaline aqueous solution. When there is too much content of this organic solvent, developability will fall and the image development remainder of the unexposed part in the said process (iii) may increase.

  In the step (v), after developing with the developer, washing and drying are usually performed.

Next, the said process (vi) is a process of performing the hardening process of at least one of high energy ray irradiation and a heating to the negative pattern obtained by the said process (v), and forming a hardening pattern.
In the step (vi), when the curing process is performed by high energy ray irradiation, an electron beam, ultraviolet rays, or the like is used.
Moreover, when performing a hardening process by heating, a hotplate, oven, a furnace, etc. can be used. The heating conditions are not particularly limited, but the atmosphere is preferably an inert gas or vacuum, and the temperature is preferably 80 ° C. to 450 ° C., more preferably 300 ° C. to 450 ° C. In order to control the curing rate of the negative pattern, stepwise heating can be applied, or an atmosphere such as nitrogen gas, air, oxygen gas, or reduced pressure can be selected as necessary.
By the curing treatment, substituents and molecules having large orientation polarization are reduced in the cured film, and the ratio of pores in the film increases, so that the relative dielectric constant of the film can be reduced.

  The relative dielectric constant of the cured pattern obtained by the cured pattern forming method of the present invention is preferably 2.9 to 2.0, and more preferably 2.6 to 2.0. . By having the above dielectric constant, the cured pattern of the present invention is suitable as various film parts constituting semiconductor elements such as LSI, system LSI, DRAM, SDRAM, RDRAM, and D-RDRAM, for example, an interlayer insulating film. . In particular, it is useful for an interlayer insulating film constituting a semiconductor element including a copper damascene process.

Hereinafter, the embodiment of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples. Here, “part” and “%” are based on mass unless otherwise specified.
In addition, the weight average molecular weight (Mw) of the polymer obtained by the following synthesis example was measured by the size exclusion chromatography (SEC) method by the following conditions.
<SEC measurement conditions>
As a measurement sample, a 2-methoxyethanol solution of LiBr—H ₃ PO ₄ having a concentration of 10 mmol / L was used as a solvent, and 0.1 g of polysiloxane was added to 100 cc of 10 mmol / L LiBr—H ₃ PO _{4 in} a 2-methoxyethanol solution. What was dissolved in was used.
Standard sample: Polyethylene oxide (manufactured by WAKO)
Equipment: High-speed GPC equipment “HLC-8120GPC” (model name), manufactured by Tosoh Corporation Column: 15 cm long aqueous / polar organic solvent-based GPC column “TSK-GEL SUPER AWM-H” (made by Tosoh Corporation) 3 in series Used in conjunction with this measurement temperature: 40 ° C
Flow rate: 0.6 ml / min.
Detector: RI (built into the high-speed GPC device)

1. Production of polysiloxane [A] Synthesis Example 1
Into a nitrogen-substituted quartz three-necked flask, 2.14 g of a 20% maleic acid aqueous solution and 139.6 g of ultrapure water were added and heated to 65 ° C. Next, a solution obtained by mixing 25.7 g (0.169 mol) of tetramethoxysilane, 206.7 g (1.52 mol) of methyltrimethoxysilane, and 25.9 g of ethoxypropanol was dropped into the reaction vessel over 1 hour. Stir at 65 ° 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 440 g of a polysiloxane [A] solution shown below. The ratio a: b of the structural unit in this polysiloxane [A] was 10:90 (mol%), and Mw was 8,600.

2. Production of Polymer [B] Synthesis Example 2
In a nitrogen-substituted quartz three-necked flask, 1.04 g (0.00731 mol) of isobutyl methacrylate, 5.11 g (0.0300 mol) of tetrahydrofurfuryl methacrylate, 1,1,2,2, -tetrafluoro-6 -1.90 g (0.00325 mol) of triphenylsulfonium methacryloyloxyhexane-1-sulfonate, 1.00 g (0.00609 mol) of azobisisobutyronitrile and 30 g of 2-butanone were added, The mixture was heated and stirred for a time to obtain a solution of the methacrylic polymer [B] shown below. The solution was allowed to cool to room temperature, and then the solvent was replaced with ethoxypropanol. The ratio a: b: c of the structural unit in the obtained methacrylic polymer [B] was 18: 74: 8 (mol%), and Mw was 9,200.

3. Production and Evaluation of Negative Radiation Sensitive Resin Composition A negative radiation sensitive resin composition was produced and evaluated in the manner described below.

Comparative Example 1
100 parts by weight of polysiloxane [A], 2.25 parts by weight of triphenylsulfonium nonafluoro-n-butanesulfonate as an acid generator, and N-tert-butoxycarbonyl-2-phenylbenzimidazole as an acid diffusion controller 0.177 parts by weight, 195 parts by weight of propylene glycol momethyl ether acetate as a solvent and 363 parts by weight of ethoxypropanol were mixed to prepare a negative radiation resin composition (Q1).

Example 1
100 parts by weight of polysiloxane [A], 10 parts by weight of polymer [B], 0.177 parts by weight of N-tert-butoxycarbonyl-2-phenylbenzimidazole as an acid diffusion controller, and propylene glycol as a solvent A negative radiation resin composition (Q2) was prepared by mixing 210 parts by weight of momethyl ether acetate and 390 parts by weight of ethoxypropanol.

Comparative Example 2
100 parts by weight of polysiloxane [A], 2.25 parts by weight of triphenylsulfonium nonafluoro-n-butanesulfonate as an acid generator, and N-tert-butoxycarbonyl-2-phenylbenzimidazole as an acid diffusion controller 0.471 parts by weight, 488 parts by weight of propylene glycol momethyl ether acetate as a solvent and 647 parts by weight of ethoxypropanol were mixed to prepare a negative radiation resin composition (Q3).

Example 2
100 parts by weight of polysiloxane [A], 10 parts by weight of polymer [B], 0.471 parts by weight of N-tert-butoxycarbonyl-2-phenylbenzimidazole as an acid diffusion controller, and propylene glycol as a solvent 525 parts by weight of momethyl ether acetate and 696 parts by weight of ethoxypropanol were mixed to prepare a negative radiation resin composition (Q4).

Comparative Example 3
100 parts by weight of polysiloxane [A], 2.25 parts by weight of triphenylsulfonium nonafluoro-n-butanesulfonate as an acid generator, and N-tert-butoxycarbonyl-2-phenylbenzimidazole as an acid diffusion controller 0.471 parts by weight, 1,218 parts by weight of propylene glycol momethyl ether acetate as a solvent and 1,614 parts by weight of ethoxypropanol were mixed to prepare a negative radiation resin composition (Q5).

Example 3
100 parts by weight of polysiloxane [A], 10 parts by weight of polymer [B], 0.471 parts by weight of N-tert-butoxycarbonyl-2-phenylbenzimidazole as an acid diffusion controller, and propylene glycol as a solvent A negative radiation resin composition (Q6) was prepared by mixing 1,310 parts by weight of momethyl ether acetate and 1,736 parts by weight of ethoxypropanol.

<Evaluation items>
1. Limit resolution measurement (1) KrF exposure As a substrate, an 8-inch silicon wafer having a lower layer antireflection film “DUV42-6” (trade name, manufactured by Nissan Chemical Industries, Ltd.) having a film thickness of 60 nm formed on the surface was used. For the formation of this antireflection film, a semiconductor manufacturing apparatus “CLEAN TRACK ACT8” (model name, manufactured by Tokyo Electron Ltd.) was used.
Thereafter, using the semiconductor manufacturing apparatus, the negative radiation resin composition (Q1) or (Q2) is spin-coated on the substrate and baked (PB) at 85 ° C. for 60 seconds to obtain a film thickness. A 500 nm film was formed. Next, a KrF excimer laser exposure apparatus “NSR S203B” (model name, manufactured by NIKON) was used for this film, and NA = 0.68, σ = 0.75 to 1/2 annular illumination conditions. Exposure was through a photomask having a 100% line and space pattern. Then, PEB was performed at 85 ° C. for 60 seconds, and developed with a 2.38 mass% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 60 seconds. Then, it was washed with water and dried to form a negative pattern. Subsequently, it was cured by heating at 420 ° C. for 180 minutes in a nitrogen atmosphere to obtain a cured pattern. At this time, the minimum line width pattern resolved by the cured pattern was defined as the limit resolution. A scanning electron microscope “S-9380” (model name, manufactured by Hitachi High-Technologies Corporation) was used for measuring the line width.

(2) ArF exposure As a substrate, an 8-inch silicon wafer having a 77 nm-thick lower-layer antireflection film “ARC29A” (trade name, manufactured by Brewer Science) on the surface was used. For the formation of this antireflection film, a semiconductor manufacturing apparatus “CLEAN TRACK ACT8” (model name, manufactured by Tokyo Electron Ltd.) was used.
Thereafter, using the semiconductor manufacturing apparatus, the negative radiation resin composition (Q3) or (Q4) is spin-coated on the substrate and baked (PB) at 85 ° C. for 60 seconds to obtain a film thickness. A 220 nm film was formed. Next, an ArF excimer laser exposure apparatus “NSR S306C” (model name, manufactured by NIKON) was used for this film, and NA = 0.78, σ = 0.85 to 1/2 annular illumination conditions. Exposure was through a photomask having a 100% line and space pattern. Then, PEB was performed at 85 ° C. for 60 seconds, and developed with a 2.38 mass% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 60 seconds. Then, it was washed with water and dried to form a negative pattern. Subsequently, it was cured by heating at 420 ° C. for 180 minutes in a nitrogen atmosphere to obtain a cured pattern. At this time, the minimum line width pattern resolved by the cured pattern was defined as the limit resolution. A scanning electron microscope “S-9380” (model name, manufactured by Hitachi High-Technologies Corporation) was used for measuring the line width.

(3) Electron beam exposure (EB exposure)
As a substrate, an 8-inch silicon wafer having a 77 nm-thick lower-layer antireflection film “ARC29A” (trade name, manufactured by Brewer Science) on the surface was used. For the formation of this antireflection film, a semiconductor manufacturing apparatus “CLEAN TRACK ACT8” (model name, manufactured by Tokyo Electron Ltd.) was used.
Thereafter, using the semiconductor manufacturing apparatus, the negative radiation resin composition (Q5) or (Q6) is spin-coated on the substrate and baked (PB) at 85 ° C. for 60 seconds to obtain a film thickness. A 60 nm film was formed. Next, this film was irradiated with an electron beam under the conditions of output: 50 KeV, current density: 5.0 ampere / cm ² using a simple electron beam drawing apparatus “HL800D” (model name, manufactured by Hitachi, Ltd.). . Then, PEB was performed at 85 ° C. for 60 seconds, and developed with a 2.38 mass% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 60 seconds. Then, it was washed with water and dried to form a negative pattern. Subsequently, it was cured by heating at 420 ° C. for 180 minutes in a nitrogen atmosphere to obtain a cured pattern. At this time, the minimum line width pattern resolved by the cured pattern was defined as the limit resolution. A scanning electron microscope “S-9380” (model name, manufactured by Hitachi High-Technologies Corporation) was used for measuring the line width.

2. Relative permittivity measurement An 8-inch N-type silicon wafer having a resistivity of 0.1 Ω · cm or less was used as a substrate. Using a semiconductor manufacturing apparatus “CLEAN TRACK ACT8” (model name, manufactured by Tokyo Electron Ltd.), negative type radiation resin compositions (Q1) to (Q6) were each spin-coated on this substrate. Thereafter, baking (PB) was performed at 85 ° C. for 60 seconds to form a film having a thickness of 500 nm. Next, a KrF excimer laser immersion exposure apparatus “NSR S203B” (model name, manufactured by NIKON) was used for this film, and the wafer was passed through a photomask under the conditions of NA = 0.68 and σ = 0.75. The entire upper film was exposed. Then, PEB was performed at 85 ° C. for 60 seconds, and developed with a 2.38 mass% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 60 seconds. Then, it washed with water and dried, and it heated at 420 degreeC for 30 minute (s) in nitrogen atmosphere, and obtained the cured film.
The relative dielectric constant of the obtained cured film was measured by the CV method using “HP16451B electrode” and “HP4284A precision LCR meter” manufactured by Agilent. The measurement conditions are temperature; 200 ° C., frequency: 100 kHz. In addition, the sample for a measurement used what formed the aluminum electrode pattern by the vapor deposition method on the surface of the said cured film.

  The negative radiation-sensitive composition of the present invention forms a chemically amplified resist that is sensitive to actinic rays, for example, far ultraviolet rays typified by KrF excimer laser (wavelength 248 nm) or ArF excimer laser (wavelength 193 nm) and electron beams. It is useful as a material, has a high resolution, and gives a cured film with a low relative dielectric constant. Therefore, it can be used extremely favorably in the production of integrated circuit elements, which are expected to become increasingly finer in the future. .

Claims (9)

[A] a polysiloxane having a silanol group,
[B] a polymer having a structural unit represented by the following general formula (1) and having a weight average molecular weight of 1,000 to 100,000, and
[C] A negative radiation sensitive composition comprising a solvent.

(In the formula, R ¹ represents a hydrogen atom, a methyl group, or a trifluoromethyl group, and Z represents a group that generates an acid by radiation.)   The negative radiation-sensitive composition according to claim 1, wherein in the polymer having the structural unit represented by the general formula (1), Z is a group that becomes an anion by radiation. The negative radiation-sensitive composition according to claim 1 or 2, wherein the structural unit represented by the general formula (1) is a structural unit represented by the following general formula (2).

(In the formula, R ¹ represents a hydrogen atom, a methyl group or a trifluoromethyl group, and each R ² independently represents a hydrogen atom, a substituted or unsubstituted C 1-10 linear or branched group. Represents an alkyl group, a fluorine atom or a linear or branched perfluoroalkyl group having 1 to 10 carbon atoms, A represents a single bond or a divalent organic group, and G represents a single bond or a divalent group containing a fluorine atom. M ^{m +} represents an onium cation, m is an integer of 1 to 3, and p is an integer of 1 to 8.)   In the structural unit represented by the formula (2), A is — (CO) OA′—, A ′ is a divalent hydrocarbon group, and a divalent hydrocarbon containing at least one heteroatom. The negative radiation sensitive composition of Claim 3 which is group or a single bond. The negative radiation-sensitive composition according to claim 3 or 4, wherein in the structural unit represented by the formula (2), the R ² is a fluorine atom or a linear or branched alkyl group having 1 to 10 carbon atoms. object. The polysiloxane [A] hydrolyzes at least one selected from a hydrolyzable silane compound represented by the following general formula (3) and a hydrolyzable silane compound represented by the following general formula (4). The negative radiation-sensitive composition according to any one of claims 1 to 5, which is a polymer obtained by condensation.
R ³ _a Si (OR ⁴ ) _4-a (3)
(Wherein R ³ represents a hydrogen atom, a fluorine atom, a linear or branched alkyl group having 1 to 5 carbon atoms, a cyano group, a cyanoalkyl group, or an alkylcarbonyloxy group, and R ⁴ represents a monovalent organic group. Represents a group, and a represents an integer of 1 to 3.)
Si (OR ⁵ ) ₄ (4)
(In the formula, R ⁵ represents a monovalent organic group.)   The negative radiation sensitive composition according to any one of claims 1 to 6, wherein the content of the polymer [B] is 1 to 30 parts by mass with respect to 100 parts by mass of the polysiloxane [A]. object. Applying the negative radiation sensitive composition according to any one of claims 1 to 7 to a substrate to form a coating film (i);
A step (ii) of baking the coating film obtained by the step (i);
Exposing the film obtained by the step (ii) (iii);
A step (iv) of baking the exposed film obtained by the step (iii);
Developing the film obtained in the step (iv) with a developer to form a negative pattern (v);
A step (vi) of forming a cured pattern by subjecting the negative pattern obtained by the step (v) to at least one of high energy ray irradiation and heating;
A cured pattern forming method comprising:   A cured pattern obtained by the cured pattern forming method according to claim 8.