JP5568892B2 - Negative radiation sensitive composition, cured pattern forming method, and cured pattern - Google Patents

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 and a high elastic modulus, 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.

  In addition, in the multilayering of semiconductor elements and the like, since the flatness is required for the interlayer insulating film after electrode formation, a flattening process such as a CMP process is usually performed. Since a physical force is applied to the interlayer insulating film during the CMP process, the interlayer insulating film is required to be more elastic.

  Furthermore, since the radiation normally used in the lithography process is a single wavelength, the incident radiation and the radiation reflected at the upper and lower interfaces of the resist coating interfere with each other within the resist coating, resulting in a “standing wave effect” or A phenomenon called “multiple interference effect”, that is, even if the exposure amount is constant, if the thickness of the resist film varies, the effective exposure amount to the resist film varies due to mutual interference within the film. A phenomenon may occur and adversely affect the formation of the resist pattern. Therefore, what can be patterned without the influence of the standing wave effect is required.

  The present invention has been made in view of the above circumstances, has a radiation-sensitive property, can be patterned, can be patterned without being affected by the standing wave effect, and has good resolution. In addition, a negative radiation sensitive material suitable for forming a cured pattern constituting an interlayer insulating film having a low relative dielectric constant and a high elastic modulus, which is required as semiconductor devices and the like are further integrated and multilayered. It aims at providing the cured pattern obtained by this property composition, the cured pattern formation method using the same, and this cured pattern formation method.

〔一般式（１）において、Ｒ^１及びＲ^５は、それぞれ独立に、水素原子、フッ素原子、アルコキシル基、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す。Ｒ^２及びＲ^４は、それぞれ独立に、１価の有機基を表し、Ｒ^２及びＲ^４が複数存在する場合には、複数のＲ^２及び複数のＲ^４はそれぞれ同一でも異なっていてもよい。Ｒ^３は、単結合、アリーレン基、メチレン基、又は炭素数２〜１０のアルキレン基を表し、Ｒ^３が複数存在する場合はそれぞれ同一でも異なっていてもよい。ｂは１〜３の整数を示し、ｍは２〜２０の整数を示す。〕

〔一般式（２）において、Ｒ^６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、芳香族含有炭化水素基、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^６が複数存在する場合はそれぞれ同一でも異なっていてもよい。Ｒ^７は、１価の有機基を表し、Ｒ^７が複数存在する場合はそれぞれ同一でも異なっていてもよい。ｄは１〜３の整数である。〕
［２］前記加水分解性シラン化合物が、更に、下記一般式（３）で表される有機ケイ素化合物（ａ３）を含む前記［１］に記載のネガ型感放射線性組成物。

〔一般式（３）において、Ｒ^８は、炭素数２〜６のアルケニル基を表し、Ｒ^８が複数存在する場合はそれぞれ同一でも異なっていてもよい。Ｒ^９は、１価の有機基を表し、Ｒ^９が複数存在する場合はそれぞれ同一でも異なっていてもよい。ｅは、１〜３の整数である。〕
［３］前記加水分解性シラン化合物が、更に、下記一般式（４）で表される有機ケイ素化合物（ａ４）を含んでおり、
且つ、該有機ケイ素化合物（ａ４）の含有量が、前記有機ケイ素化合物（ａ１）１００質量部に対して、５〜５０質量部である前記［１］又は［２］に記載のネガ型感放射線性組成物。

〔一般式（４）において、Ｒ^１０は１価の有機基を表し、Ｒ^１０はそれぞれ同一でも異なっていてもよい。〕
［４］前記［１］乃至［３］のいずれか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、
前記工程（ｉ）により得られた塗膜をベークする工程（ｉｉ）と、
前記工程（ｉｉ）により得られた膜を露光する工程（ｉｉｉ）と、
前記工程（ｉｉｉ）により得られた、露光された膜をベークする工程（ｉｖ）と、
前記工程（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、
前記工程（ｖ）により得られたネガ型パターンに、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。
［５］前記工程（ｖｉ）における硬化処理が、エネルギー線照射処理である前記［４］に記載の硬化パターン形成方法。
［６］前記［４］又は［５］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 hydrolyzable silane compound comprising an organosilicon compound (a1) represented by the following general formula (1) and an organosilicon compound (a2) represented by the following general formula (2) Polysiloxane obtained by hydrolytic condensation;
(B) a radiation sensitive acid generator;
(C) a solvent;
(D) A negative radiation-sensitive composition comprising an acid diffusion inhibitor.

[In General Formula (1), R ¹ and R ⁵ are each independently a hydrogen atom, a fluorine atom, an alkoxyl group, a linear or branched alkyl group having 1 to 5 carbon atoms, a cyano group, or a cyanoalkyl group. Or an alkylcarbonyloxy group. R ² and R ⁴ each independently represent a monovalent organic group, and when a plurality of R ² and R ⁴ are present, the plurality of R ² and the plurality of R ⁴ may be the same or different. . R ³ represents a single bond, an arylene group, a methylene group, or an alkylene group having 2 to 10 carbon atoms, and when a plurality of R ³ are present, they may be the same or different. b represents an integer of 1 to 3, and m represents an integer of 2 to 20. ]

[In General Formula (2), R ⁶ represents a hydrogen atom, a fluorine atom, a linear or branched alkyl group having 1 to 5 carbon atoms, an aromatic-containing hydrocarbon group, a cyano group, a cyanoalkyl group, or an alkyl group. When a plurality of R ⁶ are present, they may be the same or different. R ⁷ represents a monovalent organic group, and when a plurality of R ⁷ are present, they may be the same or different. d is an integer of 1-3. ]
[2] The negative radiation-sensitive composition according to [1], wherein the hydrolyzable silane compound further contains an organosilicon compound (a3) represented by the following general formula (3).

[In General Formula (3), R ⁸ represents an alkenyl group having 2 to 6 carbon atoms, and when a plurality of R ⁸ are present, they may be the same or different. R ⁹ represents a monovalent organic group, and when a plurality of R ⁹ are present, they may be the same or different. e is an integer of 1 to 3. ]
[3] The hydrolyzable silane compound further contains an organosilicon compound (a4) represented by the following general formula (4):
And negative-type radiation sensitive substance as described in said [1] or [2] whose content of this organosilicon compound (a4) is 5-50 mass parts with respect to 100 mass parts of said organosilicon compounds (a1). Sex composition.

[In General Formula (4), R ¹⁰ represents a monovalent organic group, and R ¹⁰ may be the same or different. ]
[4] A step (i) of applying a negative radiation-sensitive composition according to any one of [1] to [3] to a substrate to form a coating film;
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 energy ray irradiation and heating to form a cured pattern. Forming method.
[5] The cured pattern forming method according to [4], wherein the curing process in the step (vi) is an energy ray irradiation process.
[6] A cured pattern obtained by the cured pattern forming method according to [4] or [5].

  Since the negative radiation-sensitive composition of the present invention has excellent resolution, it can be patterned finely and can be patterned without being affected by the standing wave effect, and has a low relative dielectric constant and a high elastic modulus. A hardened pattern 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 and a high elastic modulus material, and processing using a conventional interlayer insulating film. Process efficiency can be greatly improved. Furthermore, a planarization process such as a CMP process can be performed without problems.

It is explanatory drawing which shows typically the cross-sectional shape of the pattern which concerns on an Example.

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 comprises (A) polysiloxane (hereinafter referred to as “polysiloxane (A)”) and (B) generation of radiation-sensitive acid. Agent (hereinafter also referred to as “acid generator (B)”), (C) solvent (hereinafter also referred to as “solvent (C)”), and (D) acid diffusion inhibitor (hereinafter referred to as “acid diffusion”). Inhibitor (D) ").

(1-1) Polysiloxane (A)
The polysiloxane (A) includes an organosilicon compound represented by the following general formula (1) (hereinafter also referred to as “compound (a1)”) and an organosilicon compound represented by the following general formula (2) ( Hereinafter, it is also obtained by hydrolytic condensation of a hydrolyzable silane compound containing “compound (a2)”.

〔一般式（１）において、Ｒ^１及びＲ^５は、それぞれ独立に、水素原子、フッ素原子、アルコキシル基、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す。Ｒ^２及びＲ^４は、それぞれ独立に、１価の有機基を表し、Ｒ^２及びＲ^４が複数存在する場合には、複数のＲ^２及び複数のＲ^４はそれぞれ同一でも異なっていてもよい。Ｒ^３は、単結合、アリーレン基、メチレン基、又は炭素数２〜１０のアルキレン基を表し、Ｒ^３が複数存在する場合はそれぞれ同一でも異なっていてもよい。ｂは１〜３の整数を示し、ｍは２〜２０の整数を示す。〕

[In General Formula (1), R ¹ and R ⁵ are each independently a hydrogen atom, a fluorine atom, an alkoxyl group, a linear or branched alkyl group having 1 to 5 carbon atoms, a cyano group, or a cyanoalkyl group. Or an alkylcarbonyloxy group. R ² and R ⁴ each independently represent a monovalent organic group, and when a plurality of R ² and R ⁴ are present, the plurality of R ² and the plurality of R ⁴ may be the same or different. . R ³ represents a single bond, an arylene group, a methylene group, or an alkylene group having 2 to 10 carbon atoms, and when a plurality of R ³ are present, they may be the same or different. b represents an integer of 1 to 3, and m represents an integer of 2 to 20. ]

〔一般式（２）において、Ｒ^６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、芳香族含有炭化水素基、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^６が複数存在する場合はそれぞれ同一でも異なっていてもよい。Ｒ^７は、１価の有機基を表し、Ｒ^７が複数存在する場合はそれぞれ同一でも異なっていてもよい。ｄは１〜３の整数である。〕

[In General Formula (2), R ⁶ represents a hydrogen atom, a fluorine atom, a linear or branched alkyl group having 1 to 5 carbon atoms, an aromatic-containing hydrocarbon group, a cyano group, a cyanoalkyl group, or an alkyl group. When a plurality of R ⁶ are present, they may be the same or different. R ⁷ represents a monovalent organic group, and when a plurality of R ⁷ are present, they may be the same or different. d is an integer of 1-3. ]

(1-1-1) Compound (a1)
Examples of the alkoxyl group in R ¹ and R ⁵ of the general formula (1) include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, a 2-methylpropoxy group, and 1-methyl. Propoxy group, t-butoxy group, n-pentyloxy group, neopentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, 2-ethylhexyloxy group, n-nonyloxy group, n- A decyloxy group etc. can be mentioned.
Examples of the linear or branched alkyl group having 1 to ⁵ carbon atoms in R ¹ and R ⁵ 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.
Furthermore, examples of the cyanoalkyl group in R ¹ and R ⁵ include a cyanoethyl group and a cyanopropyl group.
Examples of the alkylcarbonyloxy group in R ¹ and R ⁵ include a methylcarbonyloxy group, an ethylcarbonyloxy group, a propylcarbonyloxy group, and a butylcarbonyloxy group.
R ¹ and R ⁵ may be the same or different.

Examples of the monovalent organic group in R ² and R ⁴ of the general formula (1) include alkyl ethers, alkoxyl groups, aryl groups, other aromatic-containing hydrocarbon groups, alkenyl groups; and cyclic ether structures such as glycidyl groups. And the like. Among these, an alkyl group, an alkoxyl 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.
As said alkoxyl group, a C1-C10 linear or branched alkoxyl group is mentioned. Specifically, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, 2-methylpropoxy group, 1-methylpropoxy group, t-butoxy group, n-pentyloxy group, neo Examples include pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, 2-ethylhexyloxy group, n-nonyloxy group, n-decyloxy group and 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 other aromatic-containing hydrocarbon group include a benzyl group and a phenethyl group.
Examples of the alkenyl group include a vinyl group, 1-propenyl group, 2-propenyl group (allyl group), 3-butenyl group, 3-pentenyl group, and 3-hexenyl group.
R ² and R ⁴ may be the same or different. When there are a plurality of R ² and R ⁴ (that is, when m is an integer of 2 to 20), the plurality of R ² and the plurality of R ⁴ may be the same, May be different.

As an arylene group in R < ³ > of the said General formula (1), a C6-C10 arylene group is preferable, for example. Specific examples include a phenylene group, a naphthylene group, methylphenylene, ethylphenylene, chlorophenylene group, bromophenylene group, and fluorophenylene group.
Moreover, as a C2-C10 alkylene group in R < ³ >, an ethylene group, a propylene group, a butylene group etc. are mentioned, for example.
When a plurality of R ³ are present (for example, when b is 2 or 3, or when m is an integer of 2 to 20), each R ³ may be the same or different. Also good.

Said b in the said General formula (1) is an integer of 1-3, Preferably it is 1 or 2.
The m is an integer of 2 to 20, preferably 2 to 10, and more preferably 2.

  Specific examples of the compound (a1) represented by the general formula (1) include hexamethoxydisilane, hexaethoxydisilane, hexaphenoxydisilane, 1,1,1,2,2-pentamethoxy-2-methyldisilane, 1,1,1,2,2-pentaethoxy-2-methyldisilane, 1,1,1,2,2-pentaphenoxy-2-methyldisilane, 1,1,1,2,2-pentamethoxy-2 -Ethyldisilane, 1,1,1,2,2-pentaethoxy-2-ethyldisilane, 1,1,1,2,2-pentaphenoxy-2-ethyldisilane, 1,1,1,2,2- Pentamethoxy-2-phenyldisilane, 1,1,1,2,2-pentaethoxy-2-phenyldisilane, 1,1,1,2,2-pentaphenoxy-2-phenyldisilane, 1,1,2, 2-te Lamethoxy-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;

  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-butoxysilyl) ethane, 1- (dimethoxymethylsilyl) -1- (trimeth) Sisilyl) 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-butoxy Methylsilyl) -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-propoxymethyl) Yl) -2- (tri-n-propoxysilyl) ethane, 1- (di-isopropoxymethylsilyl) -2- (tri-isopropoxysilyl) 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, bis (dimethylmethoxysilyl) methane, bis (dimethylethoxysilyl) methane, bis (dimethyl-n-propoxysilyl) methane, bis (dimethyl-isopropoxysilyl) methane, bis (dimethyl-n-butoxysilyl) methane, Bis (dimethyl-sec-butoxysilyl) methane, bis (dimethyl-tert-butoxysilyl) methane, 1,2-bis (dimethylmethoxysilyl) ethane, 1,2-bis (dimethylethoxysilyl) ethane, 1,2- Bis (dimethyl-n-propoxysilyl) ethane, 1,2-bis (dimethyl-isopropoxysilyl) ethane, 1,2-bis (dimethyl-n-butoxysilyl) ethane, 1,2-bis (dimethyl-sec- Butoxysilyl) ethane, 1,2-bis (dimethyl-tert-but Shishiriru) ethane,

  1- (dimethoxymethylsilyl) -1- (trimethylsilyl) methane, 1- (diethoxymethylsilyl) -1- (trimethylsilyl) methane, 1- (di-n-propoxymethylsilyl) -1- (trimethylsilyl) methane, 1- (di-isopropoxymethylsilyl) -1- (trimethylsilyl) methane, 1- (di-n-butoxymethylsilyl) -1- (trimethylsilyl) methane, 1- (di-sec-butoxymethylsilyl) -1 -(Trimethylsilyl) methane, 1- (di-tert-butoxymethylsilyl) -1- (trimethylsilyl) methane, 1- (dimethoxymethylsilyl) -2- (trimethylsilyl) ethane, 1- (diethoxymethylsilyl) -2 -(Trimethylsilyl) ethane, 1- (di-n-propoxymethylsilyl) -2- ( Limethylsilyl) ethane, 1- (di-isopropoxymethylsilyl) -2- (trimethylsilyl) ethane, 1- (di-n-butoxymethylsilyl) -2- (trimethylsilyl) ethane, 1- (di-sec-butoxymethyl) Silyl) -2- (trimethylsilyl) ethane, 1- (di-tert-butoxymethylsilyl) -2- (trimethylsilyl) ethane,

  1,2-bis (trimethoxysilyl) benzene, 1,2-bis (triethoxysilyl) benzene, 1,2-bis (tri-n-propoxysilyl) benzene, 1,2-bis (tri-isopropoxysilyl) ) 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-bis (tri tert-butoxysilyl) benzene, 1,4-bis (trimethoxysilyl) benzene, 1,4-bis (triethoxysilyl) benzene, 1,4-bis (tri-n-propoxysilyl) benzene, 1,4- Bis (tri-isopropoxysilyl) benzene, 1,4-bis (tri-n-butoxysilyl) benzene, 1,4-bis (tri-sec-butoxysilyl) benzene, 1,4-bis (tri-tert- Butoxysilyl) benzene and the like.

  Furthermore, polycarbosilanes such as polydimethoxymethylcarbosilane and polydiethoxymethylcarbosilane are exemplified.

  Among these compounds, 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-tetramethyldisilane, 1,2-diethoxy-1,1,2,2 -Tetramethyldisilane, 1,2-dimethoxy-1,1,2,2-tetraphenyldisilane, 1,2-diethoxy-1,1,2,2-tetraphenyldisilane, bis (trimethoxysilyl) methane, bis (Triethoxysilyl) methane, 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- (diethoxy Methylsilyl) -2- (triethoxysilyl) ethane, bis (dimethoxymethylsilyl) methane, bis (diethoxymethylsilyl) methane, 1,2-bis (dimethoxymethylsilyl) ethane, 1,2-bis (diethoxy) Methylsilyl) ethane, bis (dimethylmethoxysilyl) methane, bis (dimethylethoxysilyl) methane, 1,2-bis (dimethylmethoxysilyl) ethane, 1,2-bis (dimethylethoxysilyl) ethane, 1- (dimethoxymethyl) Silyl) -1- (trimethylsilyl) methane, 1- (diethoxymethylsilyl) 1- (trimethylsilyl) methane, 1- (dimethoxymethylsilyl) -2- (trimethylsilyl) ethane, 1- (diethoxymethylsilyl) -2- (trimethylsilyl) ethane, 1,2-bis (trimethoxysilyl) benzene, 1,2-bis (triethoxysilyl) benzene, 1,3-bis (trimethoxysilyl) benzene, 1,3-bis (triethoxysilyl) benzene, 1,4-bis (trimethoxysilyl) benzene, 1, 4-bis (triethoxysilyl) benzene, polydimethoxymethylcarbosilane, polydiethoxymethylcarbosilane and the like are preferable.

  In addition, the compound (a1) represented by the said General formula (1) may be used individually by 1 type, and may be used in combination of 2 or more type.

(1-1-2) Compound (a2)
The “linear or branched alkyl group having 1 to 5 carbon atoms”, “cyanoalkyl group” and “alkylcarbonyloxy group” in R ⁶ of the general formula (2) are each represented by the general formula (1). The description of “a linear or branched alkyl group having 1 to 5 carbon atoms”, “cyanoalkyl group”, and “alkylcarbonyloxy group” in R ¹ in FIG. The “aromatic group-containing hydrocarbon group” in R ⁶ of the general formula (2) is a monovalent organic group “aryl group” and “other aromatic group-containing hydrocarbons” in R ² of the general formula (1). The explanation of “base” can be applied as it is. When a plurality of R ⁶ are present (that is, when d is 2 or 3), all R ⁶ may be the same, or all or part of them may be different.

In addition, examples of the monovalent organic group in R ⁷ of the general formula (2) include groups having a cyclic ether structure such as an alkyl group, an aryl group, an alkenyl 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, 1-propenyl group, 2-propenyl group (allyl group), 3-butenyl group, 3-pentenyl group, and 3-hexenyl group.
When a plurality of R ⁷ are present (that is, when d is 1 or 2), all R ⁷ may be the same, or all or part of them may be different.

  Specific examples of the compound (a2) represented by the general formula (2) 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 Run, 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 compounds (a2), methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-isopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxy Silane, diethyldimethoxysilane, diethyldiethoxysilane and the like are preferable.
In addition, the compound (a2) represented by the general formula (2) may be used alone or in combination of two or more.

(1-1-3) Other compound (a3)
The hydrolyzable silane compound for obtaining the polysiloxane (A) may contain only the compounds (a1) and (a2), and is represented by the following general formula (3) as necessary. An organic silicon compound (hereinafter also referred to as “compound (a3)”) may be further included.

〔一般式（３）において、Ｒ^８は、炭素数２〜６のアルケニル基を表し、Ｒ^８が複数存在する場合はそれぞれ同一でも異なっていてもよい。Ｒ^９は、１価の有機基を表し、Ｒ^９が複数存在する場合はそれぞれ同一でも異なっていてもよい。ｅは、１〜３の整数である。〕

[In General Formula (3), R ⁸ represents an alkenyl group having 2 to 6 carbon atoms, and when a plurality of R ⁸ are present, they may be the same or different. R ⁹ represents a monovalent organic group, and when a plurality of R ⁹ are present, they may be the same or different. e is an integer of 1 to 3. ]

The alkenyl group having 2 to 6 carbon atoms in R ⁸ of the general formula (3) is preferably a group represented by the following general formula (i).

〔一般式（ｉ）において、ｎは０〜４の整数を示す。「＊」は、結合手を示す。〕

[In general formula (i), n shows the integer of 0-4. “*” Indicates a bond. ]

  N in the general formula (i) is an integer of 0 to 4, preferably an integer of 0 or 1, and more preferably 0.

  Examples of the alkenyl group other than the group represented by the general formula (i) include a butenyl group, a pentenyl group, and a hexenyl group.

In addition, regarding the “monovalent organic group” in R ⁹ of the general formula (3), the description of the “monovalent organic group” in R ⁷ of the general formula (2) can be applied as it is. When a plurality of R ⁹ are present (that is, when e is 1 or 2), all R ⁹ may be the same, or all or part of them may be different.

  Specific examples of the compound (a3) represented by the general formula (3) include vinyltrimethoxysilane, allyltrimethoxysilane, vinyltriethoxysilane, vinyltri-n-propoxysilane, vinyltriisopropoxysilane, vinyltri- n-butoxysilane, vinyltri-sec-butoxysilane, vinyltri-tert-butoxysilane, vinyltriphenoxysilane, allyltrimethoxysilane, allyltri-n-propoxysilane, allyltriisopropoxysilane, allyltri-n-butoxysilane, allyltri -Sec-butoxysilane, allyltri-tert-butoxysilane, allyltriphenoxysilane and the like.

Of these compounds (a3), vinyltrimethoxysilane, allyltrimethoxysilane, vinyltriethoxysilane, allyltriethoxysilane, and the like are preferable.
In addition, the compound (a3) represented by the said General formula (3) may be used individually by 1 type, and may be used in combination of 2 or more type.

(1-1-4) Other compound (a4)
The hydrolyzable silane compound may further contain an organosilicon compound represented by the following general formula (4) (hereinafter also referred to as “compound (a4)”) as necessary.

〔一般式（４）において、Ｒ^１０は１価の有機基を表し、Ｒ^１０はそれぞれ同一でも異なっていてもよい。〕

[In General Formula (4), R ¹⁰ represents a monovalent organic group, and R ¹⁰ may be the same or different. ]

With respect to the “monovalent organic group” in R ¹⁰ of the general formula (4), the description of the “monovalent organic group” in R ⁷ of the general formula (2) can be applied as it is. Incidentally, it may be all each R ¹⁰ is the same, may be different for all or part.

Examples of the compound (a4) 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, the compound (a4) represented by the said General formula (4) may be used individually by 1 type, and may be used in combination of 2 or more type.

(1-1-5) Properties of polysiloxane (A) The content ratio of the structural unit derived from the compound (a1) in the polysiloxane (A) is the sum of all the structural units contained in the polysiloxane (A). Is preferably 5 to 50 mol%, more preferably 5 to 30 and even more preferably 5 to 20 mol%. When this content ratio is 5 to 50 mol%, a rectangular pattern in which standing waves are hard to be generated is obtained, and a cured pattern having a high elastic modulus can be obtained.
Further, the content ratio of the structural unit derived from the compound (a2) is preferably 5 to 95 mol% when the total of all the structural units contained in the polysiloxane (A) is 100 mol%, More preferably, it is 20-90, More preferably, it is 30-90 mol%. When this content is 5 to 95 mol%, when forming a litho pattern, the negative radiation-sensitive composition in the unexposed area with respect to the developer has good solubility, and the exposed area pattern is difficult to peel off. Therefore, it is preferable.
Furthermore, the total of the structural unit derived from the compound (a1) and the structural unit derived from the compound (a2) is 50 to 100 when the total of all the structural units contained in the polysiloxane (A) is 100 mol%. It is preferable that it is mol%, More preferably, it is 70-100 mol%, More preferably, it is 90-100 mol%.

The weight average molecular weight (hereinafter also referred to as “Mw”) of the polysiloxane (A) is preferably 1,000 to 200,000, and 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 applicability and storage stability.
The Mw is a polystyrene equivalent value measured by gel permeation chromatography (GPC).

(1-1-6) Production Method of Polysiloxane (A) The polysiloxane (A) is a hydrolyzable silane compound, that is, the compounds (a1) to (a4) as starting materials, and the starting materials are organic. It can be produced by dissolving in a solvent, adding water intermittently or continuously to the solution, and causing 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.

  Moreover, when manufacturing polysiloxane (A) using the said outgoing compounds (a1) and (a2), the reaction ratio (molar ratio) of a compound (a1) and (a2), ie, a compound (a1) / compound ( a2) The ratio is preferably 5/95 to 95/5, more preferably 10/90 to 90/10, still more preferably 20/80 to 80/20. When this reaction ratio is 5/95 to 95/5, a rectangular pattern in which a standing wave is hardly generated is obtained.

  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, merit acid, arachidonic acid, mykimic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linolenic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzene Examples include sulfonic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, and tartaric acid.
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, diaza Bicyclononane, diazabicycloundecene, tetramethylammonium hydroxide and the like can be mentioned.
Examples of the inorganic base include ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide and the like.

Of these catalysts, metal chelate compounds, organic acids and inorganic acids are preferred.
Moreover, these catalysts may be used individually by 1 type, and may be used in combination of 2 or more type.

  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, it is possible to obtain a composition having excellent coating properties and excellent storage stability.
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 boiling point of the reaction by-product is lower than the boiling point of the organic solvent. , It can be distilled off under reduced pressure.

  Moreover, 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 in one kind or two or more kinds.

(1-2) Acid generator (B)
The acid generator (B) generates an acid upon exposure, and the resin component is cross-linked by the action of the acid generated by the exposure. As a result, the exposed portion of the resist film becomes hardly soluble in an alkali developer. It has the function of forming a negative resist pattern.
Examples of the acid generator (B) include onium salts such as sulfonium salts and iodonium salts, organic halogen compounds, sulfone compounds such as disulfones and diazomethane sulfones, and the like.

Preferable specific examples of the acid generator (B) include, for example, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium perfluoro-n-octanesulfonate, triphenylsulfonium 2- Bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, triphenylsulfonium 2- (3-tetracyclo [4.4.0.1 ^2,5 .1 ^{7 , 10} ] dodecanyl) -1,1-difluoroethanesulfonate, triphenylsulfonium salt compounds such as triphenylsulfonium N, N′-bis (nonafluoro-n-butanesulfonyl) imidate, triphenylsulfonium camphorsulfonate;

4-cyclohexylphenyldiphenylsulfonium trifluoromethanesulfonate, 4-cyclohexylphenyldiphenylsulfonium nonafluoro-n-butanesulfonate, 4-cyclohexylphenyldiphenylsulfonium perfluoro-n-octanesulfonate, 4-cyclohexylphenyldiphenylsulfonium 2-bicyclo [2. 2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, 4-cyclohexyl-phenyl diphenyl sulfonium 2- (3-tetracyclo ^[4.4.0.1 2,5 ^{.1 7, 10]} dodecanyl) -1,1-difluoroethanesulfonate, 4-cyclohexyl-phenyl diphenyl sulfonium N, N'-bis (nonafluoro -n- butanesulfonyl) imidate 4-cyclohexyl-phenyl diphenyl sulfonium salt compounds such as 4-cyclohexyl-phenyl camphorsulfonate;

4-t-butylphenyldiphenylsulfonium trifluoromethanesulfonate, 4-t-butylphenyldiphenylsulfonium nonafluoro-n-butanesulfonate, 4-t-butylphenyldiphenylsulfonium perfluoro-n-octanesulfonate, 4-t-butylphenyl Diphenylsulfonium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, 4-t-butylphenyldiphenylsulfonium 2- (3-tetracyclo [4.4. 0.1 ^2,5 .1 ^7,10] dodecanyl) -1,1-difluoroethanesulfonate, 4-t-butylphenyl diphenyl sulfonium N, N'-bis (nonafluoro -n- butanesulfonyl) imidate, 4-t- Butylphenyl 4-t-butylphenyl diphenyl sulfonium salt compounds such as triphenylsulfonium camphorsulfonate;

Tri (4-t-butylphenyl) sulfonium trifluoromethanesulfonate, tri (4-t-butylphenyl) sulfonium nonafluoro-n-butanesulfonate, tri (4-t-butylphenyl) sulfonium perfluoro-n-octanesulfonate, Tri (4-t-butylphenyl) sulfonium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, tri (4-t-butylphenyl) sulfonium 2 - (3-tetracyclo ^[4.4.0.1 2,5 ^{.1 7,10]} dodecanyl) -1,1-difluoroethanesulfonate, tri (4-t- butylphenyl) sulfonium N, N'-bis (nonafluoro -N-butanesulfonyl) imidate, tri (4-t-butylphenyl) sulfur Bromide tri (4-t- butylphenyl) such as camphorsulfonate sulfonium salt compound;

Diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium perfluoro-n-octanesulfonate, diphenyliodonium 2-bicyclo [2.2.1] hept-2-yl-1,1,2, 2-tetrafluoroethane sulfonate, diphenyliodonium 2- (3-tetracyclo ^[4.4.0.1 2,5 ^{.1 7,10]} dodecanyl) -1,1-difluoroethanesulfonate, diphenyliodonium N, N'-bis Diphenyliodonium salt compounds such as (nonafluoro-n-butanesulfonyl) imidate, diphenyliodonium camphorsulfonate;

Bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium nonafluoro-n-butanesulfonate, bis (4-t-butylphenyl) iodonium perfluoro-n-octanesulfonate, Bis (4-t-butylphenyl) iodonium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, bis (4-t-butylphenyl) iodonium 2 - (3-tetracyclo ^[4.4.0.1 2,5 ^{.1 7,10]} dodecanyl) -1,1-difluoroethanesulfonate, bis (4-t- butylphenyl) iodonium N, N'-bis (nonafluoro -N-butanesulfonyl) imidate, bis (4-t-butylphenyl) io Bis (4-t- butylphenyl) such as camphorsulfonate iodonium salt compounds;

1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, (4-n-Butoxynaphthalen-1-yl) tetrahydrothiophenium perfluoro-n-octanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium 2-bicyclo [2.2. 1] Hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium 2- (3-tetracyclo [4.4. 0.1 ^2,5 .1 ^7,10 ] dodecanyl) -1,1-difluoroethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium N, N′-bis (nonafluoro-n-butanesulfonyl) imidate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothio 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium salt compounds such as phenium camphorsulfonate;

1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, (3,5-Dimethyl-4-hydroxyphenyl) tetrahydrothiophenium perfluoro-n-octanesulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium 2-bicyclo [2.2. 1] Hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium 2- (3-tetracyclo [4.4. 0.1 ^2,5 .1 ^7,10 ] dodecanyl) -1,1-difluoro Ethanesulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium N, N′-bis (nonafluoro-n-butanesulfonyl) imidate, 1- (3,5-dimethyl-4-hydroxyphenyl) ) 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium salt compounds such as tetrahydrothiophenium camphorsulfonate;

N- (trifluoromethanesulfonyloxy) succinimide, N- (nonafluoro-n-butanesulfonyloxy) succinimide, N- (perfluoro-n-octanesulfonyloxy) succinimide, N- (2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethane sulfonyloxy) succinimide, N- (2- (3- tetracyclo ^[4.4.0.1 2,5 ^{.1 7,10]} dodecanyl) Succinimide compounds such as -1,1-difluoroethanesulfonyloxy) succinimide and N- (camphorsulfonyloxy) succinimide;

N- (trifluoromethanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (nonafluoro-n-butanesulfonyloxy) bicyclo [2.2.1] hept -5-ene-2,3-dicarboximide, N- (perfluoro-n-octanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- ( 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy imide, N- (2- (3- tetracyclo ^[4.4.0.1 2,5 ^{.1 7,10]} dodecanyl) -1,1-difluoroethane-sulfonyloxy) bicyclo [2.2.1] hept Bicyclo [2.2.1] such as -5-ene-2,3-dicarboximide, N- (camphorsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide. And hept-5-ene-2,3-dicarboximide compounds.

  In the negative radiation-sensitive composition of the present invention, the acid generator (B) may be included alone or in combination of two or more.

  Content of the said acid generator (B) contained in the negative radiation sensitive composition of this invention is 0.1-30 mass parts with respect to 100 mass parts of said polysiloxane (A). More preferably, it is 0.1-20 mass parts, More preferably, it is 0.1-15 mass parts. When this content is 0.1 to 30 parts by mass, it is preferable in terms of sensitivity, resolution, and pattern shape.

(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, a halogen-containing solvent, etc. Is mentioned.
In the negative radiation-sensitive composition of the present invention, components such as the polysiloxane (A), the acid generator (B), and the acid diffusion inhibitor (D) described later are dissolved or dispersed in the solvent (C). Has been included.

Examples of the alcohol solvent include a monoalcohol solvent, a polyhydric alcohol solvent, a polyhydric alcohol partial ether solvent, and the like.
Examples of the monoalcohol solvent 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- Descriptor decyl alcohol, furfuryl alcohol, phenol, cyclohexanol, methyl cyclohexanol, 3,3,5-trimethyl cyclohexanol, benzyl alcohol, diacetone alcohol and the like.

  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- Examples include hexanediol, 2,4-heptanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, and tripropylene glycol.

  Examples of the polyhydric alcohol partial ether solvent 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-ethylbutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, Propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, and the like.

  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.

  Examples of the amide solvent 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.

  Examples of the ether solvent 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-ethyl Butyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, di Tylene glycol 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, di Phenyl ether, anisole, and the like.

  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. N-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methyl pentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methyl cyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, Ethyl acetoacetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol acetate 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, malonic acid Examples include diethyl, dimethyl phthalate, and diethyl phthalate.

Examples of the aliphatic hydrocarbon solvent include n-pentane, isopentane, n-hexane, isohexane, n-heptane, isoheptane, 2,2,4-trimethylpentane, n-octane, isooctane, cyclohexane, methylcyclohexane and the like. Is mentioned.
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 trimethylbenzene.
Examples of the halogen-containing solvent include dichloromethane, chloroform, chlorofluorocarbon, chlorobenzene, dichlorobenzene, and the like.

  These solvents (C) may be used alone or in combination of two or more, regardless of the type.

As the solvent (C), when forming a cured pattern using the negative radiation-sensitive composition of the present invention, after baking (PB) the coating film, from the viewpoint of reducing the amount of residual solvent in the film, 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) Acid diffusion inhibitor (D)
The acid diffusion inhibitor (D) controls the diffusion phenomenon of the acid in the resist film caused by exposure to ultraviolet rays or the like on the dry film obtained by using the negative radiation-sensitive composition of the present invention. It is a component which has the effect | action which suppresses the undesirable chemical reaction in.
By adding such an acid diffusion inhibitor (D), 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. And extremely excellent process stability can be obtained.

The acid diffusion inhibitor (D) 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.

  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- Tri (cyclo) alkylamines such as octylamine, tri-n-nonylamine, tri-n-decylamine, cyclohexyldimethylamine, dicyclohexylmethylamine, tricyclohexylamine; aniline, N-methylaniline, N, N-dimethylaniline, Aromatic amines such as 2-methylaniline, 3-methylaniline, 4-methylaniline, 4-nitroaniline, 2,6-dimethylaniline, 2,6-diisopropylaniline, diphenylamine, triphenylamine, naphthylamine; triethanol Amines, Alkanolamines such as ethanolaniline; 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-dimethylamino ester) Le) ether, bis (2-diethylaminoethyl) ether.

  Examples of the amide group-containing compound include N-tert-butoxycarbonyldi-n-octylamine, N-tert-butoxycarbonyldi-n-nonylamine, N-tert-butoxycarbonyldi-n-decylamine, and N-tert. -Butoxycarbonyldicyclohexylamine, 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-butoxycarbonyl-1,12-diaminododecane, N, N'-di-tert-butoxycarbonyl-4,4'-diaminodiphenylmethane, N-tert-butoxycarbonylbenzimidazole, N-tert-butoxycarbonyl-2 -Methylbenzimidazole, N-tert-butoxycarbonyl-2-fur N-tert-butoxy such as nilbenzimidazole, N-tert-butoxycarbonyl-pyrrolidine, N-tert-butoxycarbonyl-piperidine, N-tert-butoxycarbonyl-4-hydroxy-piperidine, N-tert-butoxycarbonyl-morpholine In addition to carbonyl group-containing amino compounds, formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide, pyrrolidone, N-methylpyrrolidone, etc. It is done.

  Examples of the quaternary ammonium hydroxide compound include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-propylammonium hydroxide, tetra-n-butylammonium hydroxide, and the like.

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

  These acid diffusion inhibitors (D) may be used alone or in combination of two or more, regardless of the type.

  As the acid diffusion inhibitor (D), 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.

  The content of the acid diffusion inhibitor (D) contained in the negative radiation-sensitive composition of the present invention is usually 15 parts by mass or less, preferably 10 parts by mass with respect to 100 parts by mass of the polysiloxane (A). Part or less, more preferably 5 parts by weight 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.

(1-5) Additive The negative radiation-sensitive composition of the present invention may contain an additive such as a surfactant.
The said surfactant is a component which has the effect | action which improves the applicability | paintability of the negative radiation sensitive composition of this invention, striation, the developability after exposure, etc.
As this surfactant, nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, silicone surfactants, polyalkylene oxide surfactants, fluorine surfactants, Examples include poly (meth) acrylate surfactants.

Examples of the nonionic surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene n-octylphenyl ether, polyoxyethylene n-nonylphenyl ether, polyethylene glycol dilaurate. And polyethylene glycol 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 Co., Ltd.),“ Megafax F171 ”,“ "Megafax F173" (manufactured by Dainippon Ink and 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.).

Of these surfactants, fluorine-based surfactants and silicone-based surfactants are preferable.
In addition, these surfactants 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.

(1-6) Method for Producing Negative Type Radiation Sensitive Composition The negative type radiation sensitive composition of the present invention comprises the polysiloxane (A), the acid generator (B), the solvent (C), It can be obtained by mixing the acid diffusion inhibitor (D) and the additive used as necessary by a known method.
Further, the solid content concentration of the negative radiation composition of the present invention (concentration of all components excluding the solvent (C)) is appropriately selected according to the purpose, use, etc., for example, 1 to 50 mass. %, 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 includes a step (i) of applying the negative radiation-sensitive composition of the present invention to a substrate to form a coating film, and the step (i) The step (ii) for baking the coating film obtained by the step (ii), the step (iii) for exposing the film obtained by the step (ii), and the exposed film obtained by the step (iii). The step (iv) of baking, the step (v) of developing the film obtained by the step (iv) with a developer to form a negative pattern, and the negative pattern obtained by the step (v) And (vi) forming a cured pattern by applying at least one of energy beam irradiation and heating.

In 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 by 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). The 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. , Ethyldimethylamine, 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. Of these compounds, tetramethylammonium hydroxide is particularly preferable.
In addition, these may be used individually by 1 type and may be used in combination of 2 or more type.

  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.

Further, 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, alcohols such as n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, tert-butyl alcohol, cyclopentanol, cyclohexanol, 1,4-hexanediol, 1,4-hexanedimethylol; ethers such as tetrahydrofuran and dioxane And the like; esters such as ethyl acetate, n-butyl acetate and isoamyl acetate; aromatic hydrocarbons such as toluene and xylene; and phenol and dimethylformamide. These organic solvents may be used individually by 1 type, and may be used in combination of 2 or more type.

  When the developer contains an organic solvent, the content 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 may fall and the image development residue 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 step (vi) is a step of forming a cured pattern by applying at least one of energy ray irradiation and heating to the negative pattern obtained in the step (v).
The curing treatment in the step (vi) is preferably energy irradiation among energy beam irradiation and heating.

  In this step (vi), when curing is performed by energy beam 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. Moreover, it is preferable that heating temperature is 80-450 degreeC, More preferably, it is 300-450 degreeC. 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 such a 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 lowered.

  Moreover, the process (II-1) which forms a negative type | mold hole pattern board | substrate which apply | coats, exposes, and develops a negative type radiation sensitive composition on a board | substrate using the pattern formation method of this invention, and has a negative type | mold hole pattern; A negative radiation sensitive composition is applied, exposed and developed on the obtained negative hole pattern substrate, a negative trench pattern is formed on the negative hole pattern substrate, and a negative dual damascene pattern substrate is formed. Step (II-2) of forming and a step of forming a cured pattern having a dual damascene structure by subjecting the obtained negative type dual damascene pattern substrate to at least one treatment of high energy ray irradiation and heating ( It is also possible to form a dual damascene structure by performing II-3).

About the application process of the negative radiation sensitive composition in the said process (II-1) and (II-2), an exposure process, and the image development process, respectively, the process (i) in the formation method of the above-mentioned hardening pattern, The explanations of (iii) and (iv) can be applied. Moreover, you may provide the process (refer the process (ii) in the formation method of the above-mentioned hardening pattern) of baking a coating film between an application | coating process and an exposure process.
Moreover, about the hardening process in the said process (II-3), description of the process (v) in the formation method of the above-mentioned hardening pattern is applicable.

The relative dielectric constant of the cured pattern obtained by the cured pattern forming method of the present invention is preferably 1.5 to 4.5, more preferably 2.0 to 3.5.
Moreover, it is preferable that the elasticity modulus of the hardening pattern obtained by the hardening pattern formation method of this invention is 5 GPa or more, More preferably, it is 10 GPa or more.
When the relative dielectric constant and the elastic modulus are within the above ranges, the cured pattern of the present invention can be used for various film portions constituting semiconductor elements such as LSI, system LSI, DRAM, SDRAM, RDRAM, and D-RDRAM, for example, It can be suitably used as 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>
Using a GPC column (2 G2000HXL, 1 G3000HXL, 1 G4000HXL) manufactured by Tosoh Corporation, flow rate: 1.0 mL / min. Measurement was performed by gel permeation chromatography (GPC) using monodisperse polystyrene as a standard under the analysis conditions of elution solvent: tetrahydrofuran, column temperature: 40 ° C., detector: RI (built in the high-speed GPC apparatus).

[1] Production of polysiloxane (A) Using the following organosilicon compounds, polysiloxanes (A-1) to (A-11) and (AR-1) to (AR-2) were synthesized as follows. did.
<Organic silicon compound (a1)>
(A1-1): Compound having the following structure [bis (trimethoxysilyl) methane]

(A1-2): Compound having the following structure [bis (dimethylmethoxysilyl) methane]

(A1-3): Compound having the following structure [bis (dimethoxymethylsilyl) methane]

(A1-4): Compound having the following structure [1- (dimethoxymethylsilyl) -1- (trimethylsilyl) methane]

(A1-5): compounds of the following structure (poly dimethoxymethyl polycarbosilane, Si side of the terminal methoxy group, and CH ₂ side of the terminal trimethoxysilyl group, n: 8)

(A1-6): Compound of the following structure [1,2-bis (triethoxysilyl) ethane]

(A1-7): Compound of the following structure [1,2-bis (dimethoxymethylsilyl) ethane]

(A1-8): Compound having the following structure [1- (dimethoxymethylsilyl) -2- (trimethylsilyl) ethane]

(A1-9): Compound of the following structure [1,2-bis (dimethylmethoxysilyl) ethane]

(A1-10): Compound having the following structure [1,4-bis (trimethoxysilyl) benzene]

<Organic silicon compound (a2)>
(A2-1): Methyltrimethoxysilane <organosilicon compound (a3)>
(A3-1): Vinyltrimethoxysilane <organosilicon compound (a4)>
(A4-1): Tetramethoxysilane

(1) Synthesis of polysiloxane (A-1) In a nitrogen-substituted flask, 82 parts of methyltrimethoxysilane (a2-1), 53 parts of bis (triethoxysilyl) ethane (a1-6), and propylene glycol After 92 parts of monoethyl ether was added and the reaction solution was heated to 65 ° C. in a water bath, 1 part of a 20% maleic acid aqueous solution and 72 parts of ultrapure water were added and stirred at 65 ° C. for 2 hours. This reaction liquid was returned to room temperature and concentrated under reduced pressure until the solid content concentration became 30% to obtain polysiloxane (A-1). The content ratio [(a2-1) :( a1-6)] of each constituent monomer in the polysiloxane (A-1) was [80:20] (mol%), and Mw was 3000.

(2) Synthesis of polysiloxanes (A-2) to (A-14), (AR-1) and (AR-2) In the amount of ultrapure water shown in Table 1 below, the types shown in Table 1 below and The polysiloxanes (A-2) to (A-14), (AR- 1) and (AR-2) were synthesized.
In Table 1, Mw of each polysiloxane is also shown. Further, the content ratio of the constituent monomer in each polysiloxane [theoretical value (mol%) determined by the amount of each monomer used] is as follows.
<Polysiloxane (A-2)>
[(A4-1) :( a2-1) :( a1-1)] = [10:70:20]
<Polysiloxane (A-3)>
[(A2-1) :( a3-1) :( a1-6)] = [40:30:30]
<Polysiloxane (A-4)>
[(A4-1) :( a2-1) :( a1-2)] = [15:70:15]
<Polysiloxane (A-5)>
[(A2-1) :( a1-3)] = [80:20]
<Polysiloxane (A-6)>
[(A2-1) :( a1-4)] = [80:20]
<Polysiloxane (A-7)>
[(A2-1) :( a1-5)] = [80:20]
<Polysiloxane (A-8)>
[(A4-1) :( a2-1) :( a1-7)] = [10:70:20]
<Polysiloxane (A-9)>
[(A3-1) :( a2-1) :( a1-8)] = [10:70:20]
<Polysiloxane (A-10)>
[(A3-1) :( a2-1) :( a1-9)] = [10:70:20]
<Polysiloxane (A-11)>
[(A2-1) :( a1-10)] = [80:20]
<Polysiloxane (A-12)>
[(A2-1) :( a1-6)] = [95: 5]
<Polysiloxane (A-13)>
[(A2-1) :( a1-6)] = [90:10]
<Polysiloxane (A-14)>
[(A2-1) :( a1-6)] = [50:50]
<Polysiloxane (AR-1)>
(A4-1) :( a2-1)] = [80:20]
<Polysiloxane (AR-2)>
(A4-1) :( a2-1)] = [5:95]

[2] Preparation of negative radiation sensitive resin composition <Example 1>
100 parts of polysiloxane (A) [the polysiloxane (A-1)], 2 parts of acid generator (B) [(B-2): triphenylsulfonium nonafluoro-n-butanesulfonate], and acid diffusion inhibition Agent (D) [(D-1): 2-phenylbenzimidazole] 0.02 part and solvent (C) [(C-1): propylene glycol moethyl ether] to a solid content concentration of 17% Thus, a negative radiation resin composition of Example 1 was prepared.

<Examples 2-14 and Comparative Examples 1-2>
Each negative radiation resin composition of Examples 2 to 14 and Comparative Examples 1 to 2 was the same as Example 1 except that the various components shown in Table 2 were blended in the amounts shown in Table 2. Solid content concentration: 17%) was prepared.

The details of each component in Table 2 are as follows.
<Acid generator (B)>
(B-1): Triphenylsulfonium 2- (bicyclo [2.2.1] hepta-2′-yl) -1,1,2,2-tetrafluoroethanesulfonate (B-2): Triphenylsulfonium nona Fluoro-n-butanesulfonate <Solvent (C)>
(C-1): Propylene glycol monoethyl ether <Acid diffusion inhibitor (D)>
(D-1): 2-Phenylbenzimidazole

[3] Evaluation of negative type radiation sensitive composition About each composition of Examples 1-14 and Comparative Examples 1-2, various evaluation of following (1)-(4) is performed as follows, and the result is shown. It is shown in Table 3.

(1) Limit resolution measurement <KrF exposure>
An 8-inch silicon wafer was used as the substrate. Then, using the semiconductor manufacturing apparatus “CLEAN TRACK ACT8” (model name, manufactured by Tokyo Electron Ltd.), the negative radiation resin compositions of Examples 1 to 14 and Comparative Examples 1 and 2 were spun onto the substrate. A film having a thickness of 500 nm was formed by coating and baking (PB) at 85 ° C. for 60 seconds. 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.

<ArF exposure>
An 8-inch silicon wafer was used as the substrate. Then, using a semiconductor manufacturing apparatus “CLEAN TRACK ACT8” (model name, manufactured by Tokyo Electron Ltd.), the negative radiation resin composition of Example 1 was spin-coated on the substrate and baked at 85 ° C. for 60 seconds. By performing (PB), a film having a thickness of 220 nm 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.

(2) Influence of pattern shape and standing wave The cross-sectional shape of the line and space pattern (1L1S) having a line width of 300 nm of the cured pattern formed in the same manner as in (1) was observed. In this case, when (a), (b) or (c) in the cross-sectional shape shown in FIG. 1 is “good”, a T-top shape or a round top shape (that is, a shape other than a rectangle) is indicated as “bad”. ".
Moreover, the influence of the standing wave in the cross-sectional shape shown in FIG. 1 evaluated (a), (b) or (c) as “good” and (d), (e) or (f) as “bad”.
A scanning electron microscope (manufactured by Hitachi High-Technologies Corporation, “S-4800”) was used for the observation of the cross-sectional shape.

(3) Relative permittivity measurement As a substrate, an 8-inch N-type silicon wafer having a resistivity of 0.1 Ω · cm or less was used. Then, using a semiconductor manufacturing apparatus “CLEAN TRACK ACT8” (model name, manufactured by Tokyo Electron Ltd.), the negative radiation resin compositions of Examples 1 to 14 and Comparative Examples 1 and 2 were spun onto the substrate. The film was coated and baked (PB) at 85 ° C. for 60 seconds to form a film having a thickness of 500 nm. Next, the entire surface of the wafer was exposed to this film without using a mask under the conditions of NA = 0.68 and σ = 0.75 using a KrF excimer laser immersion exposure apparatus (“NSR S203B”, manufactured by NIKON). . 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 obtained the whole surface film without a negative pattern.
Next, as shown in Table 3, the entire surface film was subjected to a curing treatment according to the following method (i), (ii) or (iii) to obtain a cured film.
Thereafter, an aluminum electrode pattern was formed on the obtained cured film by a vapor deposition method to prepare a sample for measuring relative permittivity. With respect to this sample, the relative dielectric constant of the cured film at 200 ° C. was measured at a frequency of 100 kHz by the CV method using “HP16451B electrode” and “HP4284A precision LCR meter” manufactured by Agilent.
(I) Heat treatment The entire film was heated at 420 ° C. for 1 hour under vacuum.
(Ii) Ultraviolet irradiation The whole surface film was irradiated with ultraviolet rays for 8 minutes while heating the coating film at 400 ° C. on a hot plate in a chamber having an oxygen partial pressure of 0.01 kPa. As the ultraviolet light source, white ultraviolet light having a wavelength of 250 nm or less was used. Since this ultraviolet ray is white ultraviolet ray, the illuminance cannot be measured by an effective method.
(Iii)
The whole surface film was irradiated for 4 minutes under an irradiation dose of 300 μC / cm ² and an acceleration voltage of 7 kev while heating the film at 350 ° C. on a hot plate in a chamber having an oxygen partial pressure of 0.01 kPa. did.

(4) Measurement of elastic modulus (Young's modulus) To the cured film obtained by the same method as in (3) above, a Berkovich indenter was attached to an ultra-small hardness meter (Nanoindentator XP) manufactured by MTS, and the continuous rigidity The elastic modulus of the cured film was measured by a measurement method.

[4] Evaluation of Examples According to Table 3, when the negative radiation sensitive compositions of Examples 1 to 14 were used, patterning was possible without the influence of the standing wave effect, and the relative dielectric constant was It was found that a cured pattern having a low elastic modulus can be formed.

  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 such as 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, has a low relative dielectric constant, and has a high elastic modulus, so it is extremely suitable for the manufacture of integrated circuit elements that are expected to become increasingly finer in the future. Can be used for

Claims (6)

(A) Hydrolytic condensation of a hydrolyzable silane compound containing an organosilicon compound (a1) represented by the following general formula (1) and an organosilicon compound (a2) represented by the following general formula (2) Polysiloxane obtained by
(B) a radiation sensitive acid generator;
(C) a solvent;
(D) A negative radiation-sensitive composition comprising an acid diffusion inhibitor.

[In General Formula (1), R ¹ and R ⁵ are each independently a hydrogen atom, a fluorine atom, an alkoxyl group, a linear or branched alkyl group having 1 to 5 carbon atoms, a cyano group, or a cyanoalkyl group. Or an alkylcarbonyloxy group. R ² and R ⁴ each independently represent a monovalent organic group, and when a plurality of R ² and R ⁴ are present, the plurality of R ² and the plurality of R ⁴ may be the same or different. . R ³ represents a single bond, an arylene group, a methylene group, or an alkylene group having 2 to 10 carbon atoms, and when a plurality of R ³ are present, they may be the same or different. b represents an integer of 1 to 3, and m represents an integer of 2 to 20. ]

[In General Formula (2), R ⁶ represents a hydrogen atom, a fluorine atom, a linear or branched alkyl group having 1 to 5 carbon atoms, an aromatic-containing hydrocarbon group, a cyano group, a cyanoalkyl group, or an alkyl group. When a plurality of R ⁶ are present, they may be the same or different. R ⁷ represents a monovalent organic group, and when a plurality of R ⁷ are present, they may be the same or different. d is an integer of 1-3. ] The negative radiation-sensitive composition according to claim 1, wherein the hydrolyzable silane compound further contains an organosilicon compound (a3) represented by the following general formula (3).

[In General Formula (3), R ⁸ represents an alkenyl group having 2 to 6 carbon atoms, and when a plurality of R ⁸ are present, they may be the same or different. R ⁹ represents a monovalent organic group, and when a plurality of R ⁹ are present, they may be the same or different. e is an integer of 1 to 3. ] The hydrolyzable silane compound further contains an organosilicon compound (a4) represented by the following general formula (4),
And negative-type radiation sensitive composition of Claim 1 or 2 whose content of this organosilicon compound (a4) is 5-50 mass parts with respect to 100 mass parts of said organosilicon compounds (a1). .

[In General Formula (4), R ¹⁰ represents a monovalent organic group, and R ¹⁰ may be the same or different. ] Applying the negative radiation sensitive composition according to any one of claims 1 to 3 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 energy ray irradiation and heating to form a cured pattern. Forming method.   The curing pattern forming method according to claim 4, wherein the curing process in the step (vi) is an energy beam irradiation process.   A cured pattern obtained by the cured pattern forming method according to claim 4 or 5.

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