JP2011154214A - Negative radiation-sensitive composition, cured pattern forming method and cured pattern - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a negative radiation-sensitive composition which has high resolution and allows fine holes to be formd and allows a cured pattern with a good elastic modulus and a low relative dielectric constant to be formed, and to provide a cured pattern obtained using the negative radiation-sensitive composition, and a method for forming the cured pattern. <P>SOLUTION: The negative radiation-sensitive composition contains a polysiloxane, a radiation-sensitive acid generator, a polymer having a repeating unit represented by general formula (CI), and a solvent, wherein R<SP>1</SP>denotes H, methyl or trifluoromethyl; R<SP>2</SP>denotes a single bond, methylene, 2-5C alkylene, alkyleneoxy or alkylenecarbonyloxy; and X denotes a monovalent group having a lactone structure or a cyclic carbonate structure. <P>COPYRIGHT: (C)2011,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, a negative-type radiation-sensitive composition having high resolution, capable of forming fine pores, good elastic modulus, and capable of forming a cured pattern having a low relative dielectric constant, and using the same It is related with the hardening pattern and its formation method.

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, an interlayer insulating film having a low relative dielectric constant called polyorganosiloxane called organic SOG has also been developed (see, for example, Patent Documents 2 to 4).

Japanese Patent Laid-Open No. 5-36684 Japanese Patent Laid-Open No. 2003-3120 JP 2005-213492 A JP 2001-181506 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 and a better elastic modulus. Is now required.

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. , A negative radiation sensitive composition suitable for forming a cured pattern constituting an interlayer insulating film having a low relative dielectric constant and a high elastic modulus, a cured pattern forming method using the same, and the cured pattern It aims at providing the hardening pattern obtained by the formation method.

The present invention is as follows.
[1] (A) polysiloxane;
(B) a radiation sensitive acid generator;
(C) a polymer having a repeating unit represented by the following general formula (CI);
(D) A negative radiation-sensitive composition comprising a solvent.
[In General Formula (CI), R ¹ represents a hydrogen atom, a methyl group, or a trifluoromethyl group. R ² represents a single bond, a methylene group, an alkylene group having 2 to 5 carbon atoms, an alkyleneoxy group or an alkylenecarbonyloxy group. X represents a monovalent group having a lactone structure or a cyclic carbonate structure. ]
[2] The polymer (C) having at least one repeating unit selected from the following general formulas (C1) to (C4) as the repeating unit represented by the general formula (CI) [1] Negative-type radiation-sensitive composition as described in 1.
[In General Formulas (C1) to (C4), R ¹ represents a hydrogen atom, a methyl group or a trifluoromethyl group. R ² represents a single bond, a methylene group, an alkylene group having 2 to 5 carbon atoms, an alkyleneoxy group or an alkylenecarbonyloxy group. R ³ represents a linear or branched alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an alkylcarbonyloxy group having 1 to 12 carbon atoms, or a hydroxyalkyl group. R ⁴ represents an oxygen atom or a methylene group. A represents a trivalent organic group. l shows the integer of 1-3. m represents 0 or 1; ]
[3] Hydrolyzable silane in which the polysiloxane (A) includes an organosilicon compound (a1) represented by the following general formula (1) and an organosilicon compound (a2) represented by the following general formula (2) The negative radiation-sensitive composition according to [1], which is a polysiloxane obtained by hydrolytic condensation of a compound.
[In General Formula (1), R ¹¹ is a hydrogen atom, a fluorine atom, a linear or branched alkyl group having 1 to 5 carbon atoms, a linear or branched fluoroalkyl group having 1 to 5 carbon atoms, A cyano group, a cyanoalkyl group, or an alkylcarbonyloxy group is shown. R ¹² represents a monovalent organic group. a represents an integer of 1 to 3. ]
[In General Formula (2), R ¹³ represents a monovalent organic group. ]
[4] The negative radiation-sensitive composition according to [3], wherein R ¹¹ in the general formula (1) is a methyl group.
[5] The negative radiation-sensitive composition according to [1], wherein the weight average molecular weight in terms of polystyrene by gel permeation column chromatography of the (A) polysiloxane is 4,000 to 200,000.
[6] The negative radiation sensitive material according to [1], wherein the content of the (B) radiation sensitive acid generator is 1 to 30 parts by mass with respect to 100 parts by mass of the (A) polysiloxane. Composition.
[7] The negative radiation-sensitive composition according to [1], further comprising (E) an acid diffusion inhibitor.
[8] The negative radiation-sensitive composition according to [1], wherein the content of the polymer (C) is 1 to 70 parts by mass with respect to 100 parts by mass of the (A) polysiloxane.
[9] The negative radiation-sensitive composition according to [1], wherein the negative radiation-sensitive composition is for forming a low dielectric constant film that can be patterned by radiation.
[10] A step (i) of applying a negative radiation sensitive composition according to [1] 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 high energy ray irradiation and heating to form a cured pattern. Pattern formation method.
[11] A cured pattern obtained by the cured pattern forming method according to [10].
[12] A cured pattern obtained by the negative radiation sensitive composition according to [1].
[13] The cured pattern according to [12], wherein the relative dielectric constant is 1.5 to 3.
[14] (II-1) A step of forming a negative hole pattern substrate having a negative hole pattern by applying, exposing and developing the negative radiation sensitive composition according to [1] to a substrate;
(II-2) On the obtained negative hole pattern substrate, the negative radiation sensitive composition according to the above [1] is applied, exposed and developed, and a negative trench is formed on the negative hole pattern substrate. Forming a pattern and forming a negative dual damascene pattern substrate;
(II-3) The obtained negative dual damascene pattern substrate is subjected to at least one of high energy ray irradiation and heating to form a cured pattern having a dual damascene structure. A cured pattern forming method.
[15] A cured pattern obtained by the cured pattern forming method according to [14].
[16] The cured pattern according to [15], wherein the relative dielectric constant is 1.5 to 3.

  The negative radiation-sensitive composition of the present invention has a high resolution, can be finely patterned, can form fine pores (pores), has a low dielectric constant, and a high elastic modulus cured pattern. It can be formed easily. Therefore, it can be used not only as a material for microfabrication of semiconductor elements such as LSI, system LSI, DRAM, SDRAM, RDRAM, and D-RDRAM, but also as a material for forming a low dielectric constant film such as an interlayer insulating film. In particular, it is useful for semiconductor devices including a copper damascene process. 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, and a processing process using a conventional interlayer insulating film. The efficiency of can be greatly improved.

It is explanatory drawing which shows typically the formation method of the hardening pattern which has a dual damascene structure. It is an image which shows the cross section of the negative pattern which has a dual damascene structure.

  Hereinafter, the present invention will be described in detail. In the present specification, “(meth) acryl” means acryl and methacryl, and “(meth) acrylate” means acrylate and methacrylate.

[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) polymer (hereinafter also referred to as “polymer (C)”), (D) solvent (hereinafter referred to as “solvent (D)”. ) ")).

(1-1) Polysiloxane (A)
Although the said polysiloxane (A) in this invention is not specifically limited, For example, the organosilicon compound (henceforth "compound (a1)") represented by the following general formula (1), the following general formula (2) (Hereinafter also referred to as “compound (a2)”), an organosilicon compound represented by the following general formula (3) (hereinafter also referred to as “compound (a3)”), and the following. What was obtained by hydrolytic condensation of a hydrolyzable silane compound containing at least one compound selected from the organosilicon compounds represented by the general formula (4) (hereinafter also referred to as “compound (a4)”) Is mentioned.
Specifically, for example, a compound obtained by hydrolytic condensation of a hydrolyzable silane compound containing at least [I] compound (a1) and compound (a2), [II] compound (a1), and compound It is preferably obtained by hydrolytic condensation of a hydrolyzable silane compound containing at least (a3).
In particular, [i] obtained by hydrolytic condensation of a hydrolyzable silane compound containing only compound (a1) and compound (a2), [ii] hydrolysis containing only compound (a1) and compound (a3) It is preferable that it is obtained by hydrolytic condensation of a functional silane compound.

[In General Formula (1), R ¹¹ is a hydrogen atom, a fluorine atom, a linear or branched alkyl group having 1 to 5 carbon atoms, a linear or branched fluoroalkyl group having 1 to 5 carbon atoms, A cyano group, a cyanoalkyl group, or an alkylcarbonyloxy group is shown. R ¹² represents a monovalent organic group. a represents an integer of 1 to 3. ]

[In General Formula (2), R ¹³ represents a monovalent organic group. ]

[In the general formula (3), R ^{14 to} R ¹⁷ are the same or different and each represents a monovalent organic group. b shows the number of 0-2. c shows the number of 0-2. R ¹⁸ represents an oxygen atom, a phenylene group, or a group represented by — (CH ₂ ) _n — (wherein n is an integer of 1 to 6). d represents 0 or 1. ]

[In General Formula (4), R ¹⁹ represents an alkenyl group having 2 to 6 carbon atoms, R ²⁰ represents a monovalent organic group, and e represents an integer of 1 to 3. ]

(1-1-1) Compound (a1)
Examples of the linear or branched alkyl group having 1 to 5 carbon atoms in R ¹¹ of the general formula (1) include a methyl group, an ethyl group, a propyl group, and a butyl group. Among these, a methyl group is preferable.
Examples of the linear or branched fluoroalkyl group having 1 to 5 carbon atoms in R ¹¹ include those in which one or two or more hydrogen atoms in the alkyl group are substituted with fluorine atoms.
Furthermore, the carbon number of the alkyl moiety of the cyanoalkyl group in R ¹¹ is not particularly limited, but preferably 1 to 5 carbon atoms. Examples of the cyanoalkyl group include a cyanoethyl group and a cyanopropyl group.
The number of carbon atoms in the alkyl moiety of the alkylcarbonyloxy group in R ¹¹ is not particularly limited, but preferably 1 to 5 carbon atoms. Examples of the alkylcarbonyloxy group include a methylcarbonyloxy group, an ethylcarbonyloxy group, a propylcarbonyloxy group, and a butylcarbonyloxy group.
In addition, when there are a plurality of R ¹¹ (that is, when a in the general formula (1) is 2 or 3), each R ¹¹ may be all the same or all or a part may be different. Good.

Moreover, as a monovalent organic group in R < ¹² > of the said General formula (1), an alkyl group, an alkenyl group, an aryl group, an allyl group, a glycidyl group etc. are mentioned. 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.
The number of carbon atoms of the alkenyl group is not particularly limited, but preferably 2 to 6 carbon atoms. 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.
Although carbon number of the said aryl group is not specifically limited, C6-C12 is preferable. 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.
When a plurality of R ¹² are present (that is, when a in general formula (1) is 1 or 2), each R ¹² may be all the same, or all or a part may be different. Good.

  Specific examples of the compound (a1) represented by the general formula (1) 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 (a1), methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-isopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxy Silane, diethyldimethoxysilane, diethyldiethoxysilane 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)
Regarding the “monovalent organic group” in R ¹³ of the general formula (2), the description of the “monovalent organic group” in R ¹² of the general formula (1) can be applied as it is. Incidentally, it may be each R ¹³ is all the same, may be different for all or part.

Examples of the compound (a2) represented by the general formula (2) 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 (a2) represented by the general formula (2) may be used alone or in combination of two or more.

(1-1-3) Compound (a3)
Regarding the “monovalent organic group” in R ^{14 to} R ¹⁷ of the general formula (3), the description of the “monovalent organic group” in R ¹² of the general formula (1) can be applied as it is.
In a case where R ¹⁴ there are a plurality, it may be the R ¹⁴ are all the same, may be different for all or part. The same applies to R ^{15 to} R ¹⁷ .

  Specific examples of the compound represented by the general formula (3) and d = 0 include, for example, 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, , 1,1,2,2-pentamethoxy-2-phenyldisilane, 1,1,1,2,2-pentaethoxy-2-phenyldisilane, 1,1,1,2,2-pentaphenoxy-2- Phenyl Silane, 1,1,2,2-tetramethoxy-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, 1,1,2,2-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, 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-tetra Methyldisilane, 1,2-dimethoxy-1,1,2,2-tetraphenyldisilane, 1,2-diethoxy-1,1,2,2-tetraphenyldisilane and the like are preferable.

  Furthermore, specific examples of the compound represented by the general formula (3) and d = 1 include, for example, 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, , 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 ( Li-tert-butoxysilyl) 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- (die Xoxymethylsilyl) -2- (triethoxysilyl) ethane, 1- (di-n-propoxymethylsilyl) -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, 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, bis (trimethoxysilyl) methane, bis (triethoxysilyl) methane, 1,2-bis (trimethoxysilyl) ethane, 1,2-bis (triethoxysilyl) ethane, 1- (dimethoxymethyl) Silyl) -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-bis (trimethoxysilyl) benzene, 1,2-bis (trie Xylsilyl) 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 preferred.
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) Compound (a4)
The alkenyl group having 2 to 6 carbon atoms in R ¹⁹ of the general formula (4) is preferably a group represented by the following general formula (i).

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

  N in the said general formula (i) is an integer of 0-4, Preferably it is an integer of 0-2, More preferably, it is 0 or 1.

  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 ²⁰ of the general formula (4), the description of the “monovalent organic group” in R ¹² of the general formula (1) can be applied as it is. When a plurality of R ²⁰ are present (that is, when e in general formula (4) is 1 or 2), each R ²⁰ may be all the same, or all or part of them may be different. Also good.

  Specific examples of the compound (a4) represented by the general formula (4) include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri-n-propoxysilane, vinyltriisopropoxysilane, vinyltri-n-butoxysilane, Vinyltri-sec-butoxysilane, vinyltri-tert-butoxysilane, vinyltriphenoxysilane, allyltrimethoxysilane, allyltriethoxysilane, allyltri-n-propoxysilane, allyltriisopropoxysilane, allyltri-n-butoxysilane, allyltri -Sec-butoxysilane, allyltri-tert-butoxysilane, allyltriphenoxysilane and the like.

Of these compounds (a4), vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane and the like 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 95 mol% or less, more preferably 10 to 95 mol%, still more preferably 20 to 90 mol%, and particularly preferably 30 to 90 mol%. When this content is 95 mol% or less, when forming a litho pattern, the negative radiation-sensitive composition in the unexposed area in the developer has good solubility, and the pattern in the exposed area is less likely to collapse. preferable.

  The content ratio of the structural unit derived from the compound (a2) is 30 mol% or less, more preferably 1 to 30 mol%, when the total of all the structural units contained in the polysiloxane (A) is 100 mol%. More preferably, it is 5 to 30 mol%, particularly preferably 5 to 20 mol%. When this content ratio is 30 mol% or less, when forming a litho pattern, the negative radiation-sensitive composition in the unexposed area in the developer is good in solubility and the exposed area pattern is not easily collapsed. preferable.

  The content ratio of the structural unit derived from the compound (a3) is preferably 30 mol% or less, more preferably, when the total of all the structural units contained in the polysiloxane (A) is 100 mol%. It is 5-30 mol%, More preferably, it is 5-20 mol%. When the content ratio is 30 mol% or less, the film shrinkage (pattern shrinkage) after the curing treatment is relatively small and the pattern of the exposed portion is not easily collapsed, which is preferable.

  The content ratio of the structural unit derived from the compound (a4) is preferably 60 mol% or less, more preferably, when the total of all the structural units contained in the polysiloxane (A) is 100 mol%. It is 5-50 mol%, More preferably, it is 10-40 mol%. When the content ratio is 60 mol% or less, film shrinkage (pattern shrinkage) after the curing treatment is relatively small, which is preferable.

  When the compound (a1) and the compound (a2) are used as the hydrolyzable silane compound, the total of the structural unit derived from the compound (a1) and the structural unit derived from the compound (a2) is polysiloxane ( When the total of all the structural units contained in A) is 100 mol%, it is preferably 10 to 100 mol%, more preferably 30 to 100 mol%, still more preferably 50 to 100 mol%. . When the total content is 10 to 100 mol%, when forming a litho pattern, the negative-type radiation-sensitive composition in the unexposed part in the developer has good solubility, and the pattern in the exposed part is It is preferable because it does not fall easily.

  When the compound (a1) and the compound (a3) are used as the hydrolyzable silane compound, the total of the structural unit derived from the compound (a1) and the structural unit derived from the compound (a3) is polysiloxane ( When the total of all the structural units contained in A) is 100 mol%, it is preferably 10 to 100 mol%, more preferably 30 to 100 mol%, still more preferably 50 to 100 mol%. . When the total content is 10 to 100 mol%, when forming a litho pattern, the negative-type radiation-sensitive composition in the unexposed part in the developer has good solubility, and the pattern in the exposed part is It is preferable because it does not fall easily.

Further, the carbon atom content in the polysiloxane (A) is preferably 8 to 40 atom%, more preferably when the total number of atoms constituting the polysiloxane (A) is 100 atom%. Is 8 to 20 atomic%. When the content is less than 8 atomic%, it is difficult to obtain a film having a sufficiently low relative dielectric constant when a silica-based film is formed using a radiation-sensitive composition containing polysiloxane (A). There is. On the other hand, when it exceeds 40 atomic%, film shrinkage (pattern shrinkage) after the curing treatment is large, and it may be difficult to obtain a desired pattern.
The content (atomic%) of carbon atoms in the polysiloxane (A) is determined by silanol which is obtained by completely hydrolyzing the hydrolyzable group of the component (hydrolyzable silane compound) used in 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 weight average molecular weight (hereinafter also referred to as “Mw”) of the polysiloxane (A) is preferably 4,000 to 200,000, and more preferably 7,000 to 200,000. When this Mw exceeds 200,000, gelation tends to occur. On the other hand, if it is less than 4,000, problems are likely to occur in coating properties 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.

For example, when the polysiloxane (A) is produced using the compounds (a1) and (a2), the reaction ratio (molar ratio) of the compounds (a1) and (a2), that is, the compound (a1) / compound (a2). ) Ratio is preferably 5/95 to 95/5, more preferably 10/90 to 90/10, still more preferably 90/10. When this reaction ratio is 5/95 to 95/5, 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 collapses. It is preferable because it is difficult.
When the polysiloxane (A) is produced using the compounds (a1) and (a3), the reaction ratio (molar ratio) of the compounds (a1) and (a3), that is, the compound (a1) / compound (a3). The ratio is preferably 5/95 to 95/5, more preferably 10/90 to 95/5, and still more preferably 20/80 to 95/5. When this reaction ratio is 5/95 to 95/5, 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 collapses. It is preferable because it is difficult.

  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 (D) 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) in the present invention generates an acid upon exposure, and the resin component is cross-linked by the action of the acid generated by exposure, so that the exposed portion of the resist film is difficult to be an alkaline developer. It becomes soluble and 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.

  The content of the acid generator (B) contained in the negative radiation-sensitive composition of the present invention is preferably 1 to 30 parts by mass with respect to 100 parts by mass of the polysiloxane (A). More preferably, it is 0.1-20 mass parts, More preferably, it is 0.1-15 mass parts. When this content is 1 to 30 parts by mass, the sensitivity and resolution are good, which is preferable.

(1-3) Polymer (C)
The polymer (C) in the present invention is capable of forming voids in the resulting film by decomposing at the time of film formation, and as a result, has an effect of reducing the relative dielectric constant.
This polymer (C) is a repeating unit represented by the following general formula (CI) [hereinafter referred to as “repeating unit (CI)”. ] In addition, this repeating unit (CI) may be contained only 1 type in the polymer (C), and may be contained 2 or more types.

[In General Formula (CI), R ¹ represents a hydrogen atom, a methyl group, or a trifluoromethyl group. R ² represents a single bond, a methylene group, an alkylene group having 2 to 5 carbon atoms, an alkyleneoxy group or an alkylenecarbonyloxy group. X represents a monovalent group having a lactone structure or a cyclic carbonate structure. ]

The alkylene group having 2 to 5 carbon atoms in R ² of the general formula (CI) may be linear or branched. Examples of the alkylene group include an ethylene group, a propylene group, a 1-methylethylene group, and a butylene group.
Further, alkyleneoxy group in R ² may be a branched be linear, it is preferably 1 to 10 carbon atoms. Examples of the alkyleneoxy group include an ethyleneoxy group, a propyleneoxy group, a 1-methylethyleneoxy group, and a butyleneoxy group.
Furthermore, the alkylenecarbonyloxy group in R ² may be linear or branched, and preferably has 1 to 10 carbon atoms. Examples of the alkylenecarbonyloxy group include ethylenecarbonyloxy group, trimethylenecarbonyloxy group, 1-methyl-trimethylenecarbonyloxy group, 2-methyl-trimethylenecarbonyloxy group, tetramethylenecarbonyloxy group, pentamethylenecarbonyl An oxy group etc. are mentioned.

  As the repeating unit (CI), the polymer (C) preferably has at least one repeating unit selected from the following general formulas (C1) to (C4) (hereinafter, these repeating units are respectively represented as: , “Repeating unit (C1)”, “Repeating unit (C2)”, “Repeating unit (C3)”, and “Repeating unit (C4)”).

[In General Formulas (C1) to (C4), R ¹ represents a hydrogen atom, a methyl group or a trifluoromethyl group. R ² represents a single bond, a methylene group, an alkylene group having 2 to 5 carbon atoms, an alkyleneoxy group or an alkylenecarbonyloxy group. R ³ represents a linear or branched alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an alkylcarbonyloxy group having 1 to 12 carbon atoms, or a hydroxyalkyl group. R ⁴ represents an oxygen atom or a methylene group. A represents a trivalent organic group. l shows the integer of 1-3. m represents 0 or 1; ]

Regarding R ² in the general formulas (C1) to (C4), the description of R ² in the general formula (CI) can be applied as it is.
Moreover, as a C1-C12 linear or branched alkyl group in R < ³ > of general formula (C2) and (C3), a methyl group, an ethyl group, n-butyl group, 2-methylpropyl is mentioned, for example Group, 1-methylpropyl group, tert-butyl group, n-pentyl group and the like. Among these, a methyl group, an ethyl group, an n-butyl group, and a tert-butyl group are preferable.
The number of carbon atoms of the cycloalkyl group in R ³ is not particularly limited, but preferably 3 to 25 carbon atoms. Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, an adamantyl group, and a norbornyl group.
Furthermore, as a C1-C12 alkylcarbonyloxy group in said R < ³ >, a methylcarbonyloxy group, an ethylcarbonyloxy group, a propylcarbonyloxy group, a butylcarbonyloxy group etc. are mentioned, for example.
Further, the number of carbon atoms of the hydroxyalkyl group in R ³ is not particularly limited, but is preferably 1 to 12 carbon atoms. Examples of the hydroxyalkyl group include a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, a hydroxybutyl group, a hydroxypentyl group, a hydroxyhexyl group, and a hydroxyheptyl group.

  Examples of A in the general formula (C4) include linear, branched, or cyclic trivalent hydrocarbon groups, and trivalent groups having a heterocyclic structure. These groups may be substituted with a halogen atom, a hydroxyl group, an alkoxyl group, a phenoxy group or the like.

  Moreover, as a monomer which gives the said repeating unit (C1)-(C4), each compound etc. which are represented with the following general formula (m-C1)-(m-C4) etc. can be mentioned, for example.

Note that R ^{1 to} R ⁴ , A, l, and m in the general formulas (m-C1) to (m-C4) have the same definitions as those in the general formulas (C1) to (C4).

As a preferable compound represented by the general formula (m-C1), for example, (meth) acrylic acid-5-oxo-4-oxatricyclo [4.2.1.0 ^3,7 ] nona-2 -Yl ester, (meth) acrylic acid-9-methoxycarbonyl-5-oxo-4-oxa-tricyclo [4.2.1.0 ^3,7 ] non-2-yl ester, (meth) acrylic acid-5 -Oxo-4-oxatricyclo [5.2.1.0 ^3,8 ] dec-2-yl ester, (meth) acrylic acid-10-methoxycarbonyl-5-oxo-4-oxatricyclo [ 5.2.1.0 ^3,8 ] non-2-yl ester, (meth) acrylic acid-6-oxo-7-oxabicyclo [3.2.1] oct-2-yl ester, (meth) Acrylic acid-4-methoxycarbonyl-6 Oxo-7-oxa-bicyclo [3.2.1] oct-2-yl ester, (meth) acrylic acid-7-oxo-8-oxa-bicyclo [3.3.1] oct-2-yl ester, (Meth) acrylic acid-4-methoxycarbonyl-7-oxo-8-oxabicyclo [3.3.1] oct-2-yl ester, (meth) acrylic acid-2-oxotetrahydropyran-4-yl ester , (Meth) acrylic acid-4-methyl-2-oxotetrahydropyran-4-yl ester, (meth) acrylic acid-4-ethyl-2-oxotetrahydropyran-4-yl ester, (meth) acrylic acid-4 -Propyl-2-oxotetrahydropyran-4-yl ester, (meth) acrylic acid-5-oxotetrahydrofuran-3-yl ester, (meth) acrylic acid Rylic acid-2,2-dimethyl-5-oxotetrahydrofuran-3-yl ester, (meth) acrylic acid-4,4-dimethyl-5-oxotetrahydrofuran-3-yl ester, (meth) acrylic acid-2-oxo Tetrahydrofuran-3-yl ester, (meth) acrylic acid-4,4-dimethyl-2-oxotetrahydrofuran-3-yl ester, (meth) acrylic acid-5,5-dimethyl-2-oxotetrahydrofuran-3-yl ester , (Meth) acrylic acid-2-oxotetrahydrofuran-3-yl ester, (meth) acrylic acid-5-oxotetrahydrofuran-2-ylmethyl ester, (meth) acrylic acid-3,3-dimethyl-5-oxotetrahydrofuran -2-ylmethyl ester, (meth) acrylic acid-4,4-dimethyl -5-oxo-tetrahydrofuran-2-yl methyl ester.
In addition, these compounds may be used individually by 1 type, and may be used in combination of 2 or more type.

Preferred examples of the compound represented by the general formula (m-C2) include α-methacrylic acid-γ-butyrolactone, α-methacrylic acid-β-hydroxymethyl-γ-butyrolactone, and α-methacrylic acid-β-methyl. -Γ-butyrolactone, α-methacrylic acid-β-ethyl-γ-butyrolactone, α-methacrylic acid-β-methoxy-γ-butyrolactone, α-hydroxymethyl-β-methacrylic acid-γ-butyrolactone, α-methyl-β -Methacrylic acid-γ-butyrolactone, α-ethyl-β-methacrylic acid-γ-butyrolactone, α-methacrylic acid-δ-mevalonolactone, and the like.
In addition, these compounds may be used individually by 1 type, and may be used in combination of 2 or more type.

  Preferred examples of the compound represented by the general formula (m-C3) include compounds represented by the following formulas (m-C3-1) to (m-C3-6). In addition, these compounds may be used individually by 1 type, and may be used in combination of 2 or more type.

[In the formulas (m-C3-1) to (m-C3-6), R ¹ represents a hydrogen atom, a methyl group or a trifluoromethyl group. ]

  Preferred examples of the compound represented by the general formula (m-C4) include compounds represented by the following formulas (m-C4-1) to (m-C4-21). In addition, these compounds may be used individually by 1 type, and may be used in combination of 2 or more type.

[In the formulas (m-C4-1) to (m-C4-21), R ¹ represents a hydrogen atom, a methyl group or a trifluoromethyl group. ]

  In addition to the repeating unit (CI), the polymer (C) includes a repeating unit (CII) represented by the following general formula (CII) and a repeating unit (CIII) represented by the following general formula (CIII). ) May be further included. One of these repeating units (CII) and (CIII) may be contained in the polymer (C), or two or more thereof may be contained.

[In General Formula (CII), R ⁵ represents a hydrogen atom, a methyl group or a trifluoromethyl group. R ⁶ represents a branched alkyl group. ]

[In General Formula (CIII), R ⁷ represents a hydrogen atom, a methyl group or a trifluoromethyl group. R ⁸ represents an alkylene group. ]

As the branched alkyl group of R ⁶ in the general formula (CII), for example, a branched alkyl group having 3 to 20 carbon atoms is preferable. Specific examples include an isopropyl group and an isobutyl group.

  Examples of the monomer that gives the repeating unit (CII) include compounds represented by the following general formula (m-CII).

[In General Formula (m-CII), R ⁵ represents a hydrogen atom, a methyl group, or a trifluoromethyl group. R ⁶ represents a branched alkyl group. ]

The “branched alkyl group” of R ^{6 in} the general formula (m-CII) has the same meaning as the “branched alkyl group” of R ⁶ in the general formula (CII).

  Among the compounds represented by the general formula (m-CII), isobutyl (meth) acrylate is preferable.

As the alkylene group for R ⁸ in the general formula (CIII), for example, a linear or branched alkylene group having 2 to 20 carbon atoms is preferable. Specifically, for example, 1,1-ethylene group, 1,2-ethylene group, 1,2-propylene group, 1,3-propylene group, 1,2-butylene group, 1,3-butylene group, 1 , 4-butylene group and the like. Among these, 1,1-ethylene group, 1,2-ethylene group and the like are particularly preferable.

  Examples of the monomer that provides the repeating unit (CIII) include compounds represented by the following general formula (m-CIII).

[In General Formula (m-CIII), R ⁷ represents a hydrogen atom, a methyl group or a trifluoromethyl group. R ⁸ represents an alkylene group. ]

The “alkylene group” of R ^{8 in} the general formula (m-CIII) has the same meaning as the “alkylene group” of R ⁸ in the general formula (CIII).

  Among the compounds represented by the general formula (m-CIII), 2-hydroxyethyl methacrylate is preferable.

  The content ratio of the repeating unit (CI) is preferably 1 to 80 mol%, more preferably 1 to 80 mol%, when the total of all repeating units contained in the polymer (C) is 100 mol%. 60 mol%, more preferably 1 to 40 mol%. When this content ratio is 1 to 80 mol%, the solubility of the unexposed portion in the developer can be maintained when forming a litho pattern.

  The content of the repeating unit (CII) is preferably 1 to 90 mol%, more preferably 100 mol% when the total of all repeating units contained in the polymer (C) is 100 mol%. It is 1-80 mol%, More preferably, it is 1-50 mol%. When this content rate is 1-90 mol%, when forming a litho pattern, the solubility of the negative radiation sensitive composition of the unexposed part with respect to a developing solution can be maintained.

  Furthermore, the content ratio of the repeating unit (CIII) is preferably 1 to 90 mol%, more preferably, when the total of all repeating units contained in the polymer (C) is 100 mol%. It is 1-80 mol%, More preferably, it is 1-50 mol%. A content ratio of 1 to 90 mol% is preferable because the pattern of the exposed portion is not easily collapsed when forming a litho pattern.

The polymer (C) is, for example, radical polymerization such as hydroperoxides, dialkyl peroxides, diacyl peroxides, azo compounds, etc., with the above-mentioned respective compounds giving the repeating units (CI) to (CIII). It can manufacture by using an initiator and superposing | polymerizing in a suitable solvent in presence of a chain transfer agent as needed.
Solvents used for polymerization include alkanes such as n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane; cyclohexane, cycloheptane, cyclooctane, decalin, norbornane, etc. Cycloalkanes; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene; halogenated hydrocarbons such as chlorobutanes, bromohexanes, dichloroethanes, hexamethylene dibromide, chlorobenzene; ethyl acetate, acetic acid n Saturated carboxylic acid esters such as butyl, isobutyl acetate and methyl propionate; ketones such as 2-butanone, 4-methyl-2-pentanone and 2-heptanone; air such as tetrahydrofuran, dimethoxyethanes and diethoxyethanes And the like.
These solvents may be used alone or in combination of two or more. The reaction temperature in the polymerization is usually 40 to 120 ° C, preferably 50 to 90 ° C. The reaction time is usually 1 to 48 hours, preferably 1 to 24 hours.

It is preferable that the polystyrene conversion weight average molecular weight (henceforth "Mw") by the gel permeation chromatography (GPC) of a polymer (C) is 1000-100000, More preferably, it is 1000-50000, More preferably, it is 1000. ~ 20,000. If the Mw of the polymer (C) is less than 1000, the resolution may be deteriorated. On the other hand, if this Mw exceeds 100,000, the developability may be lowered.
Moreover, the ratio (Mw / Mn) of Mw of the polymer (C) and polystyrene-reduced number average molecular weight (hereinafter referred to as “Mn”) by GPC is usually 1 to 5, preferably 1 to 3.

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

  The content of the polymer (C) contained in the negative radiation-sensitive composition of the present invention is preferably 1 to 70 parts by mass with respect to 100 parts by mass of the polysiloxane (A). Preferably it is 1-60 mass parts, More preferably, it is 1-50 mass parts. A content of 1 to 70 parts by mass is preferable because the dielectric constant can be effectively reduced and sufficient developability can be maintained.

(1-4) Solvent (D)
The solvent (D) 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 polymer (C) are dissolved or dispersed in the solvent (D). ing.

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 (D) may be used singly or in combination of two or more, regardless of the type.

As the solvent (D), 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 solvent remaining 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 (D) 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.

(1-5) Additive The negative radiation-sensitive composition of the present invention may contain additives such as an acid diffusion inhibitor and a surfactant.
The acid diffusion inhibitor controls the phenomenon of acid diffusion in the resist film caused by exposure to ultraviolet light or the like on the dry film obtained using the negative radiation-sensitive composition of the present invention, 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 inhibitor, 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 inhibitor 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 may be used alone or in combination of two or more, regardless of the type.

  As the acid diffusion inhibitor, 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 inhibitor, the content of the acid diffusion inhibitor is usually 15 parts by mass or less, preferably 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 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” (Toray Dow Corning Silicon Co.), “KP341” (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 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) Production Method of Negative Radiation Sensitive Composition The negative radiation sensitive composition of the present invention comprises the polysiloxane (A), the acid generator (B), and the polymer (C). The solvent (D) can be obtained by mixing the additive used as necessary by a known method.
Moreover, although the solid content concentration (concentration of all components except the solvent (D)) of the negative radiation composition of the present invention is appropriately selected according to the purpose, use, etc., for example, 1 to 50 masses. %, 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 method for forming a cured pattern consisting of only one shape such as a trench or a hole (hereinafter referred to as “pattern forming method (I)”). And a method for forming a cured pattern having a dual damascene structure having both trench and hole shapes (hereinafter also referred to as “pattern formation method (II)”).

(2-1) Pattern formation method (I)
The pattern forming method (I) of the present invention comprises a step (i) of applying the negative radiation-sensitive composition of the present invention to a substrate to form a coating film, and a coating film obtained by the step (i). A step (ii), a step (iii) of exposing the film obtained by the step (ii), and a step (iv) of baking the exposed film obtained by the step (iii). The film obtained in the step (iv) is developed with a developer to form a negative pattern, and the negative pattern obtained in the step (v) is irradiated with high energy rays and heated. (Vi) which performs the hardening process of at least one of these, and forms a hardening pattern.

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 subjecting the negative pattern obtained in the step (v) to at least one of high energy ray irradiation and heating.
In the step (vi), when a 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. 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, the polymer (C) and substituents and molecules having a large orientation polarization are reduced in the cured film, and the ratio of voids (pores) in the film is increased. The rate can be reduced.
The average pore size of the formed voids is preferably 10 to 20 cm. The average pore size can be measured by the same method as in the examples described later.

(2-2) Pattern formation method (II)
In the pattern forming method (II) of the present invention, (II-1) the negative radiation sensitive composition of the present invention is applied to a substrate, exposed and developed to form a negative hole pattern substrate having a negative hole pattern. Step [hereinafter also referred to as “Step (II-1)”. (II-2) The negative-type radiation sensitive composition of the present invention is applied, exposed and developed on the obtained negative-type hole pattern substrate to form a negative-type trench pattern on the negative-type hole pattern substrate. And a step of forming a negative dual damascene pattern substrate [hereinafter also referred to as “step (II-2)”. And (II-3) a step of forming a cured pattern having a dual damascene structure by subjecting the obtained negative dual damascene pattern substrate to at least one of irradiation with high energy rays and heating [hereinafter, “ Also referred to as “step (II-3)”. ].

In the step (II-1), a negative hole pattern substrate having a negative hole pattern is obtained by appropriately performing the same steps as the steps (i) to (iv) described in the pattern forming method (I). This is a step of forming (see FIG. 1A).
The preferable film thickness of the negative hole pattern obtained here is usually 30 nm to 1000 nm.

In the step (II-2), first, a negative radiation sensitive composition is applied on the negative hole pattern substrate formed in the step (II-1), and the negative radiation sensitive composition is applied on the negative hole pattern substrate. A film derived from the composition is formed (see FIG. 1B). Here, as a method of applying the negative radiation sensitive composition, the same method as described in the step (i) in the method (1) of forming the cured pattern can be used.
Moreover, in order to form the film derived from a negative radiation sensitive composition, you may bake a film similarly to the process (ii) in the formation method (1) of the said hardening pattern.
The preferable film thickness (x in step (b) of FIG. 1) of the film derived from the negative radiation-sensitive composition obtained here is usually 30 nm to 1000 nm.
Subsequently, the film derived from the negative radiation sensitive composition is treated in the same manner as in steps (iii) and (iv) in the cured pattern forming method (1), and a negative trench is formed on the negative hole pattern substrate. A pattern is formed, and a negative dual damascene pattern substrate is formed.

  In the step (II-3), the negative dual damascene pattern substrate obtained in the step (II-2) is treated in the same manner as described in the step (v) in the cured pattern forming method (1). A cured pattern having a dual damascene structure is formed.

(2-3) Cured Pattern The relative dielectric constant of the cured pattern obtained by the pattern forming methods (I) and (II) of the present invention is preferably 1.5 to 3.0, more preferably 1. .5 to 2.7.
When the relative dielectric constant is within the above range, 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, interlayer insulating films. It can be suitably used as a low dielectric constant 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.

[1] Production of polysiloxane [polysiloxane solution] As shown in the following synthesis examples (synthesis examples 1 to 3), resin solution No. 1-3 polysiloxane solutions were prepared.

In addition, the measurement of the weight average molecular weight (Mw) of the polysiloxane obtained by each synthesis example was performed by the following method.
(Measurement of Mw)
Gel permeation based on monodisperse polystyrene using GPC columns (2 G2000HXL, 1 G3000HXL, 1 G4000HXL) manufactured by Tosoh Corporation under the analysis conditions of a flow rate of 1.0 ml / min, elution solvent tetrahydrofuran, and column temperature of 40 ° C. It was measured by an association chromatography (GPC).

(Synthesis Example 1) Resin Solution No. 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 430 g of a silicon-containing resin solution (resin solution No. 1). The resin in this resin solution is defined as a silicon-containing resin (A-1) (refer to the following formula (A-1) for the structural unit).
The constituent monomer ratio (a: b) of the silicon-containing resin (A-1) was 10:90 (mol%), and Mw was 8300.

(Synthesis Example 2) Resin Solution No. 2
Into a nitrogen-substituted quartz three-necked flask, 1.20 g of a 20% maleic acid aqueous solution and 57.01 g of ultrapure water were added and heated to 75 ° C. Next, 14.4 g (0.0946 mol) of tetramethoxysilane, 102.8 g (0.755 mol) of methyltrimethoxysilane, 14.2 g (0.0946 mol) of ethyltrimethoxysilane, and 10.4 g of ethoxypropanol were added. The mixed solution was dropped into the reaction vessel over 1 hour and stirred at 75 ° C. for 2 hours. This reaction liquid was returned to room temperature and concentrated under reduced pressure until the solid content concentration became 25% to obtain 250 g of a silicon-containing resin solution (resin solution No. 2). The resin in this resin solution is referred to as silicon-containing resin (A-2) (refer to the following formula (A-2) for the structural unit).
The constituent monomer ratio (a: b: c) of the silicon-containing resin (A-2) was 10:80:10 (mol%), and Mw was 8,600.

(Synthesis Example 3) Resin Solution No. 3
In a quartz separable flask substituted with nitrogen, 81.6 g (0.60 mol) of methyltrimethoxysilane, 53.1 g (0.15 mol) of 1,2-bis (triethoxysilyl) ethane, and propylene glycol After adding 92.3 g of monoethyl ether and heating the reaction solution to 65 ° C. in a water bath, 1.1 g of 20% maleic acid aqueous solution and 72.0 g 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 200 g of a silicon-containing resin solution (resin solution No. 3). The resin in this resin solution is referred to as silicon-containing resin (A-3) (refer to the following formula (A-3) for the structural unit).
The constituent monomer ratio a: b of the silicon-containing resin (A-3) was 80:20 (mol%), and Mw was 4200.

[2] Production of polymer (C) Using the following compounds [compounds (M-1) to (M-5)] represented by the following formula, the polymers (C-1) to (C-1) to (C-6) was synthesized.
The compounds (M-1) to (M-3) are monomers that give the above-mentioned repeating unit (CI), and the compound (M-4) is a single monomer that gives the above-mentioned repeating unit (CII). The compound (M-5) is a monomer that gives the above-mentioned repeating unit (CIII).

In addition, the weight average molecular weight (Mw) and dispersion degree (Mw / Mn) of the polymer obtained by each synthesis example were performed by the following method.
(Measurement of Mw, Mw / Mn)
About molecular weight (Mw), it measured by the method similar to Mw in the above-mentioned polysiloxane. Further, the degree of dispersion Mw / Mn was calculated from the measurement results.

(1) Synthesis of polymer (C-1) α-methacrylic acid-γ-butyrolactone [said compound (M-1)] 8.88 parts (40 mol%), isobutyl methacrylate [said compound (M-4) 11.12 parts (60 mol%) was dissolved in 30 parts of 2-butanone, and 0.99 parts (5 mol%) of azobisisobutyronitrile (AIBN) was added as a polymerization initiator. A solution was prepared.
Next, 30 parts of 2-butanone was charged into a three-necked flask equipped with a thermometer and a dropping funnel, and purged with nitrogen for 30 minutes. After purging with nitrogen, the inside of the flask was heated to 80 ° C. while stirring with a magnetic stirrer. Then, the monomer solution prepared beforehand was dripped over 3 hours using the dropping funnel. The polymerization start was carried out for 6 hours with the start of dropping as the polymerization start time. After completion of the polymerization, the polymerization solution was cooled to 30 ° C. or less by water cooling. After cooling, it was added to 400 parts of methanol, and the precipitated white powder was filtered off. The white powder separated by filtration was washed as a slurry with 80 parts of methanol. Thereafter, the white powder was filtered off and dried at 50 ° C. for 17 hours to obtain a white powder polymer (C-1). The polymer (C-1) had Mw of 10200 and Mw / Mn of 1.89.

(2) Synthesis of polymers (C-2) to (C-6) The polymer (C-1) and the polymer (C-1) described above were used except that the compounds (monomers) having the types and amounts shown in Table 1 below were used. Polymers (C-2) to (C-6) were synthesized in the same manner.
In Table 1, the molecular weight (Mw) and dispersity (Mw / Mn) of the polymers (C-1) to (C-6) are also shown.

[3] Preparation of negative radiation sensitive composition In the proportions shown in Table 2, a polysiloxane solution, (B) an acid generator, (C) a polymer, (E) an acid diffusion inhibitor, and (F ) Surfactant was mixed to prepare each of the negative radiation sensitive compositions of Examples 1 to 10 and Comparative Examples 1 and 2. These compositions were blended with propylene glycol monomethyl ether acetate as the solvent (D) so that the solid content concentration would be 10%.

The details of each component in Table 2 are as follows.
<Acid generator (B)>
(B-1): Triphenylsulfonium nonafluoro-n-butanesulfonate (B-2): 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium nonafluoro-n-butanesulfonate <acid diffusion Inhibitor (E)>
(E-1): 2-phenylbenzimidazole (E-2): N-tert-butoxycarbonyl-2-phenylbenzimidazole <Surfactant (F)>
(F-1): SH8400 FLUID (Toray Dow Corning Silicon Co.)

[4] Evaluation of negative-type radiation-sensitive composition About each composition of Examples 1-10 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) Resolution As the substrate, an 8-inch silicon wafer having a 77 nm-thick lower layer antireflection film (“ARC29A”, manufactured by Brewer Science) on the surface was used. For the formation of the antireflection film, a semiconductor manufacturing apparatus “CLEAN TRACK ACT8” (manufactured by Tokyo Electron Limited) was used.
Thereafter, each negative radiation-sensitive composition is spin-coated on the substrate by the CLEAN TRACK ACT8, and baking (PB) is performed for 60 seconds under the conditions shown in Table 3 to form a film having a thickness of 220 nm. did. Next, this film was coated with an ArF excimer laser exposure apparatus (manufactured by NIKON, “NSR S306C”) through a mask pattern under conditions of NA = 0.78 and σ = 0.85-1 / 2 annular illumination. Exposed.
And after performing PEB for 60 second on the conditions shown in Table 3, it developed for 60 second at 23 degreeC with 2.38 mass% tetramethylammonium hydroxide aqueous solution. Then, it was washed with water and dried to form a negative pattern. At this time, when the 1L1S pattern having various line widths was observed, the minimum line width pattern resolved by the pattern was defined as the limit resolution. A scanning electron microscope (manufactured by Hitachi High-Technologies Corporation, “S-9380”) 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. Next, each negative radiation-sensitive composition was spin-coated on the substrate by CLEAN TRACK ACT8, and baked (PB) under the conditions shown in Table 3 to form a film having a thickness of 600 nm. Thereafter, the entire surface of the wafer was exposed to this coating film with a KrF excimer laser immersion exposure apparatus (“NSR S203B”, manufactured by NIKON) under the conditions of NA = 0.68 and σ = 0.75 without using a mask. Then, after performing PEB on the conditions shown in Table 3, it developed with 23.degree. C. for 60 seconds with 2.38 mass% tetramethylammonium hydroxide aqueous solution, washed with water, and dried. Subsequently, it heated at 420 degreeC under nitrogen atmosphere for 30 minutes, and the cured film was obtained.
An aluminum electrode pattern was formed on the obtained cured film by a vapor deposition method, and a sample for measuring relative permittivity was prepared. 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.

(3) Measurement of elastic modulus (Young's modulus) To the cured film obtained by the same method as in (2) above, a Berkovich indenter is attached to an ultra-small hardness meter (Nanoindentator XP) manufactured by MTS, and continuous rigidity is obtained. The elastic modulus of the cured pattern was measured by a measurement method.

(4) Average pore size Toluene adsorption analysis was performed on the cured film obtained by the same method as in (2) above using Ellipsometry Posiometer [EP10, XPEQT Co.], and the average pore size (平均) was measured.

[4] Formation of cured pattern having dual damascene structure <Example 11>
A method for forming a cured pattern having a dual damascene structure will be described with reference to FIG.
(1) Step (II-1) [Refer to Step (a)]
As the substrate 1, an 8-inch silicon wafer having a lower layer antireflection film (“DUV42-6”, manufactured by Nissan Chemical Industries, Ltd.) having a film thickness of 60 nm formed on the surface was used. In addition, “CLEAN TRACK ACT8” (manufactured by Tokyo Electron Limited) was used for forming the lower antireflection film.
Next, the radiation-sensitive composition of Example 3 was spin-coated on the substrate 1 by the CLEAN TRACK ACT8, and baked (PB) at 90 ° C. for 60 seconds to form a film having a thickness of 500 nm. Formed. On this film, a KrF excimer laser exposure apparatus (“NSR S203B”, manufactured by NIKON) was passed through a mask pattern having a hole pattern under the conditions of NA = 0.68, σ = 0.75, and 1/2 annular illumination. 28 mJ / cm ² exposure. Thereafter, baking (PEB) was performed at 85 ° C. for 60 seconds, and then developed with a 2.38 mass% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 60 seconds, washed with water, and dried to form a hole having a hole diameter of 200 nm. A negative hole pattern substrate 3 having an AND space pattern (1H2S) negative hole pattern 2a was formed.
(2) Step (II-2) [Refer to Steps (b) and (c)]
The negative hole pattern substrate 3 is spin-coated with the radiation-sensitive composition of Example 3 by the CLEAN TRACK ACT8 and baked (PB) at 90 ° C. for 60 seconds, thereby obtaining a negative hole pattern substrate. A film 4 (film thickness x; 500 nm) was formed on 3. A mask pattern 5 having a line pattern is formed on this coating 4 under the conditions of NA = 0.68, σ = 0.75, and 1/2 annular illumination with a KrF excimer laser exposure apparatus (“NSR S203B”, manufactured by NIKON). Was exposed to 32 mJ / cm ² . Then, after baking (PEB) at 85 ° C. for 60 seconds, development was performed at 23 ° C. for 60 seconds with a 2.38 mass% tetramethylammonium hydroxide aqueous solution. Next, it is washed with water and dried to form a negative line pattern of a line and space pattern (1L3S) having a line width of 240 nm on the negative hole pattern substrate 3, thereby having a negative having a negative trench pattern 7a. A type dual damascene pattern substrate 8 was formed.
(3) Step (II-3) [Refer to Step (d)]
Subsequently, it heated for 30 minutes at 420 degreeC in nitrogen atmosphere, and the hardening pattern 9 which has a dual damascene structure was obtained.
Here, an image showing a cross section of a negative pattern having a dual damascene structure is shown in FIG.

[5] Evaluation of Examples According to Table 3, it was found that the greater the amount of polymer (C) added, the lower the elastic modulus and the larger the average pore size. Furthermore, when the polymer (C) contains the repeating unit (CI) derived from the compounds (M-1) to (M-3) etc., the compatibility with the polysiloxane (A) increases, It was found that it burned out rapidly during the curing, and fine pores (pores) were formed, and a higher elastic modulus could be maintained with the same addition amount than in Comparative Examples 1 and 2. Moreover, according to Examples 1-10 containing the polymer (C) which has a repeating unit (CI), it turned out that these compositions are favorable also in terms of resolution.

  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. Useful as a material. In particular, the negative radiation-sensitive composition has high resolution, can form fine pores, has a good elastic modulus, and gives a cured film with a low relative dielectric constant. Then, it can be used very suitably for the production of the integrated circuit element expected.

  DESCRIPTION OF SYMBOLS 1; Substrate, 2a; Negative hole pattern, 2b; Hole, 3; Negative hole pattern substrate, 4; Negative-type radiation-sensitive composition coating, 5; Mask (reticle), 6; Exposure, 7a; Trench pattern, 7b; trench, 8; negative dual damascene pattern substrate, 9; cured pattern having dual damascene structure, x; film thickness of coating derived from negative radiation sensitive composition.

Claims (16)

(A) polysiloxane;
(B) a radiation sensitive acid generator;
(C) a polymer having a repeating unit represented by the following general formula (CI);
(D) A negative radiation-sensitive composition comprising a solvent.
[In General Formula (CI), R ¹ represents a hydrogen atom, a methyl group, or a trifluoromethyl group. R ² represents a single bond, a methylene group, an alkylene group having 2 to 5 carbon atoms, an alkyleneoxy group or an alkylenecarbonyloxy group. X represents a monovalent group having a lactone structure or a cyclic carbonate structure. ] The negative according to claim 1, wherein the polymer (C) has at least one repeating unit selected from the following general formulas (C1) to (C4) as the repeating unit represented by the general formula (CI). Type radiation sensitive composition.
[In General Formulas (C1) to (C4), R ¹ represents a hydrogen atom, a methyl group or a trifluoromethyl group. R ² represents a single bond, a methylene group, an alkylene group having 2 to 5 carbon atoms, an alkyleneoxy group or an alkylenecarbonyloxy group. R ³ represents a linear or branched alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an alkylcarbonyloxy group having 1 to 12 carbon atoms, or a hydroxyalkyl group. R ⁴ represents an oxygen atom or a methylene group. A represents a trivalent organic group. l shows the integer of 1-3. m represents 0 or 1; ] The (A) polysiloxane hydrolyzes 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). The negative radiation-sensitive composition according to claim 1, which is a polysiloxane obtained by decomposing and condensing.
[In General Formula (1), R ¹¹ is a hydrogen atom, a fluorine atom, a linear or branched alkyl group having 1 to 5 carbon atoms, a linear or branched fluoroalkyl group having 1 to 5 carbon atoms, A cyano group, a cyanoalkyl group, or an alkylcarbonyloxy group is shown. R ¹² represents a monovalent organic group. a represents an integer of 1 to 3. ]
[In General Formula (2), R ¹³ represents a monovalent organic group. ] The negative radiation-sensitive composition according to claim 3, wherein R ¹¹ in the general formula (1) is a methyl group.   2. The negative radiation-sensitive composition according to claim 1, wherein the (A) polysiloxane has a polystyrene-equivalent weight average molecular weight by gel permeation column chromatography of 4,000 to 200,000.   2. The negative radiation-sensitive composition according to claim 1, wherein the content of the (B) radiation-sensitive acid generator is 1 to 30 parts by mass with respect to 100 parts by mass of the (A) polysiloxane.   The negative radiation-sensitive composition according to claim 1, further comprising (E) an acid diffusion inhibitor.   2. The negative radiation-sensitive composition according to claim 1, wherein the content of the (C) polymer is 1 to 70 parts by mass with respect to 100 parts by mass of the (A) polysiloxane.   The negative radiation-sensitive composition according to claim 1, wherein the negative radiation-sensitive composition is for forming a low dielectric constant film that can be patterned by radiation. Applying the negative radiation sensitive composition according to claim 1 to a substrate and forming 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 to form a cured pattern. Pattern formation method.   A cured pattern obtained by the cured pattern forming method according to claim 10.   A cured pattern obtained by the negative radiation-sensitive composition according to claim 1.   The cured pattern according to claim 12, which has a relative dielectric constant of 1.5 to 3. (II-1) applying, exposing, and developing the negative radiation-sensitive composition according to claim 1 to a substrate to form a negative hole pattern substrate having a negative hole pattern;
(II-2) On the obtained negative hole pattern substrate, the negative radiation sensitive composition according to claim 1 is applied, exposed and developed, and on the negative hole pattern substrate, a negative trench pattern is formed. Forming a negative type dual damascene pattern substrate; and
(II-3) The obtained negative dual damascene pattern substrate is subjected to at least one of high energy ray irradiation and heating to form a cured pattern having a dual damascene structure. A cured pattern forming method.   A cured pattern obtained by the cured pattern forming method according to claim 14.   The cured pattern according to claim 15, which has a relative dielectric constant of 1.5 to 3.