JP2011116758A - ORGANOSILANE COMPOUND, METHOD FOR PRODUCING THE SAME, Si-CONTAINING FILM-FORMING MATERIAL CONTAINING THE SAME AND METHOD FOR FORMING FILM - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new Si-containing film-forming material, especially the Si-containing film-forming material containing an alkylsilane compound, suitable for a PECVD (Plasma Enhanced Chemical Vapor Deposition) device. <P>SOLUTION: This Si-containing film is produced by the PECVD method by using the Si-containing film-forming material containing an organosilane compound having a structure in which at least one cyclopropyl group directly bonds with a silicon atom (a concrete example is 2,4,6-tricyclopropyl-2,4,6-trimethylcyclotrisiloxane), and the same is used as an insulation film of a semiconductor device. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a Si-containing film forming material useful for forming a low dielectric constant interlayer insulating film used in a multilayer wiring technique in logic ULSI. In particular, the present invention relates to a Si-containing film forming material suitable for plasma polymerization, a method for producing the material, and a use thereof.

  In the manufacturing technology of the integrated circuit field of the electronics industry, there is an increasing demand for high integration and high speed. In silicon ULSIs, especially logic ULSIs, the performance of wiring connecting them is a problem rather than the performance due to miniaturization of MOSFETs. That is, in order to solve the wiring delay problem associated with the multilayer wiring, it is required to reduce the wiring resistance and between the wirings and the interlayer capacitance.

  For these reasons, it is essential to introduce copper wiring with lower electrical resistance and migration resistance instead of aluminum wiring, which is currently used in most integrated circuits. Sputtering or chemical vapor deposition A process of performing copper plating after seed formation by a method (hereinafter abbreviated as CVD) is being put into practical use.

There are various proposals for low dielectric constant interlayer insulating film materials. As the prior art, silicon dioxide (SiO ₂ ), silicon nitride, phosphosilicate glass has been used for inorganic systems, and polyimide has been used for organic systems. Recently, however, a tetralayer has been previously prepared for the purpose of obtaining a more uniform interlayer insulating film. Hydrolysis of ethoxysilane monomer, that is, polycondensation to obtain SiO ₂ and proposal to use as a coating material called Spin on Glass (inorganic SOG), or polysiloxane obtained by polycondensation of organic alkoxysilane monomer to organic There are proposals for use as SOG.

  Further, as an insulating film forming method, an insulating film polymer solution is applied by a spin coating method or the like, and a coating type in which a film is formed and a plasma in a plasma enhanced chemical vapor deposition (PECVD) apparatus. There are two methods, the CVD method, in which a film is formed by polymerization.

  As a proposal of the PECVD method, for example, in Patent Document 1, a method of forming a trimethylsilane oxide thin film from trimethylsilane and oxygen by PECVD is used, and in Patent Document 2, straight lines such as methyl, ethyl, and n-propyl are used. There has been proposed a method for forming an alkyl oxide silane thin film by PECVD from an alkoxysilane having an alkynyl and aryl group such as chain alkyl and vinylphenyl. These conventional PECVD process materials have good adhesion to barrier metal and copper wiring material, but the uniformity of the film is a problem, film formation speed, relative dielectric constant There were cases where there was insufficient.

  As a proposal of PECVD using cyclic siloxane, for example, in Patent Document 3, a method using tetramethylcyclotetrasiloxane is used, and in Patent Document 4, tetraalkylcyclotetrasiloxane, tetraaminocyclotetrasiloxane, octaalkylcyclotetra. A method using siloxane or octaaminocyclotetrasiloxane has been proposed.

  In these methods, cyclic siloxane is used as a raw material compound, and while maintaining the cyclic structure in the generated thin film, it is intended to form vacancies in the generated thin film and lower the relative dielectric constant. However, according to the knowledge of the present inventor, when a PECVD film is formed using these substituted cyclic siloxanes, a thin film having a relative dielectric constant of less than 2.7 cannot be obtained. This is presumably because the cyclic siloxane compound raw material easily breaks the cyclic structure in plasma to form a chain structure and does not contribute to porosity.

  Patent Document 5 proposes a six-membered cyclic siloxane such as hexamethylcyclotrisiloxane and 1,3,5-trimethyl-1,3,5-trivinylcyclotrisiloxane, and Patent Document 6 discloses a bisbenzocyclocyclosiloxane. There is a proposal to copolymerize a butene-substituted disiloquinsan compound and 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotrisiloxane, which is an eight-membered cyclic siloxane, in a plasma atmosphere. However, according to the knowledge of the present inventor, a thin film having a relative dielectric constant of less than 2.5 cannot be obtained by the methods using cyclic siloxanes substituted with vinyl and methyl according to these proposals.

  In Patent Document 7 and Patent Document 8, a PECVD method low dielectric constant thin film forming method using a porous agent is proposed. In the former, triethoxysilane, diethoxymethylsilane, and α-terpinene, which is a porous agent, are supplied into a PECVD apparatus chamber, and after PECVD film formation, annealing is performed at a temperature of 400 ° C. or higher, and α-terpinene in the thin film is formed. We have proposed a method for reducing the dielectric constant by volatilizing the derived component to make it porous. In the latter, cyclo-1,3,5,7-tetrasilylene-2,6-dioxy-4,8-dimethylene, a vinyl furyl ether as a porous agent, and nitrous oxide as an oxidizing agent are supplied into a PECVD apparatus chamber. Then, after PECVD film formation, a method of annealing is performed at a temperature of 400 ° C. or higher to volatilize a component derived from vinyl furyl ether in the thin film to reduce the dielectric constant is proposed. Although these methods can be expected to reduce the dielectric constant due to porosity, the matrix of the thin film is destroyed because the porous material is removed from the thin film by post-processing from the thin film once formed. The composition inside the film becomes non-uniform, the mechanical strength such as rigidity and Young's modulus decreases, and the formed holes become continuous open holes, preventing the diffusion of metal components into the film. It has no problem.

  On the other hand, as a coating type proposal, although the uniformity of the film is good, three steps of coating, solvent removal, and heat treatment are necessary, which is economically disadvantageous than CVD materials, and barrier metal, wiring In many cases, adhesion to a copper wiring material, which is a material, and uniform application of a coating liquid to a miniaturized substrate structure itself are problems.

Moreover, in the coating type material, the method of using a porous material in order to implement | achieve the Ultra Low-k material whose relative dielectric constant is 2.5 or less and also 2.0 or less is proposed. Organic or inorganic material matrix readily disperse the thermally decomposed organic component particles in the method of heat treating and pore formation, silicon and oxygen by evaporating SiO ₂ ultrafine particles formed by evaporation in a gas, SiO ₂ than There is a method of forming a fine particle thin film.

  However, although these porous methods are effective for lowering the dielectric constant, the mechanical strength decreases, chemical mechanical polishing (CMP) becomes difficult, and the dielectric constant increases due to moisture absorption. And wiring corrosion could be caused.

  Therefore, the market is further seeking a well-balanced material that meets all the required performance such as low dielectric constant, sufficient mechanical strength, adhesion to barrier metal, copper diffusion prevention, plasma ashing resistance, moisture resistance, etc. As a method of satisfying these required performances with a certain degree of balance, a material having an intermediate characteristic between an organic polymer and an inorganic polymer has been proposed in an organic silane material by increasing the carbon ratio of the organic substituent to silane. .

  For example, in Patent Document 9, a coating solution obtained by hydrolyzing and condensing a silicon compound having an adamantyl group in the presence of an acidic aqueous solution by a sol-gel method is used, and an interlayer having a relative dielectric constant of 2.4 or less without being made porous. A method for obtaining an insulating film is proposed. However, this material is a coating type material, and still has the problem of the film forming method using the coating type as described above.

JP 2002-110670 A JP-A-11-288931 Japanese Patent No. 20678801 JP-A-5-279856 International Publication No. 03/019645 Pamphlet JP 2004-47873 A Japanese Patent Laid-Open No. 2005-19980 JP 2001-298023 A JP 2000-302791 A

  The present invention has been made in view of the above problems, and an object thereof is to provide a novel Si-containing film forming material, particularly an Si-containing film forming material comprising an alkylsilane compound suitable for a PECVD apparatus. And an insulating film using the same and a semiconductor device including these insulating films.

  The present inventors have found that an organosilane compound having a structure in which at least one cyclopropyl group is directly bonded to a silicon atom is suitable as a material for an insulating film, particularly a low dielectric constant interlayer insulating film for a semiconductor device. The present invention has been completed.

  That is, the present invention is as follows.

  (1) 2,4,6-tricyclopropyl-2,4,6-trimethylcyclotrisiloxane, 2,2,4,4,6,6-hexacyclopropylcyclotrisiloxane, 2,4,6,8 -Tetracyclopropyl-2,4,6,8-tetramethylcyclotetrasiloxane or 2,2,4,4,6,6,8,8-octacyclopropylcyclotetrasiloxane.

  (2) 2,4,6-tricyclopropyl-2,4,6-trimethylcyclotrisiloxane and / or 2,4,6, characterized by hydrolyzing and separating and purifying cyclopropylmethyldimethoxysilane A method for producing 8-tetracyclopropyl-2,4,6,8-tetramethylcyclotetrasiloxane.

  (3) 2,2,4,4,6,6-hexacyclopropylcyclotrisiloxane and / or 2,2,4,4, characterized in that dicyclopropyldimethoxysilane is hydrolyzed and separated and purified. A method for producing 6,6,8,8-octacyclopropylcyclotetrasiloxane.

  (4) A Si-containing film-forming material comprising the compound described in (1) above.

  (5) A method for producing a Si-containing film, characterized by using the Si-containing film forming material described in (4) above.

  (6) The manufacturing method according to (5), wherein the manufacturing method is performed by a chemical vapor deposition method.

  Details of the present invention will be described below.

  The following general formula (3)

（式中、Ｒ^１６〜Ｒ^２１は、水素原子または炭素数１〜１０の炭化水素基を表す。Ｒ^１６〜Ｒ^２１は、互いに結合し、環状構造を形成してもよい。ｆは１または２、ｇは３以上６以下の整数を表す。）で表される有機シラン化合物を含有するものは、Ｓｉ含有膜形成材料として使用できる。

(Wherein R ^{16 to} R ²¹ represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. R ^{16 to} R ²¹ may be bonded to each other to form a cyclic structure. F is 1 or 2 and g represent an integer of 3 or more and 6 or less), and those containing an organosilane compound represented by (2) can be used as a Si-containing film forming material.

  The following general formula (7)

（式中、Ｒ^１６〜Ｒ^２１は水素原子または炭素数１〜１０の炭化水素基を表わす。Ｒ^１６〜Ｒ^２１は、互いに結合して環状構造を形成してもよい。Ｒ^２３は、水素原子または炭素数１〜２０の炭化水素基を表わす。ｆは、１または２を表す。）で示される有機シラン化合物を加水分解させることにより、一般式（３）で示される有機シラン化合物を製造することができる。

(Wherein R ^{16 to} R ²¹ represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. R ^{16 to} R ²¹ may combine with each other to form a cyclic structure. R ²³ represents hydrogen. Represents an atom or a hydrocarbon group having 1 to 20 carbon atoms. F represents 1 or 2.) By hydrolyzing the organosilane compound represented by formula (3), an organosilane compound represented by the general formula (3) is produced. can do.

In the general formula (3), R ^{16 to} R ²¹ are a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and may have any of a linear structure, a branched structure, and a cyclic structure. Moreover, they may combine with each other to form a cyclic structure.

  In consideration of stable use in a PECVD apparatus, a hydrocarbon group having 1 to 5 carbon atoms is particularly preferable in that the vapor pressure of the organosilane compound does not become too low.

As examples of the hydrocarbon group R ¹⁶ to R ²¹ include, but are not limited to, 1 to 10 carbon atoms, preferably an alkyl group having 1 to 5 carbon atoms, an aryl group, an arylalkyl group, alkylaryl The group can be mentioned. R ^{16 to} R ²¹ may be the same or different.

Examples of hydrocarbon groups when R ^{16 to} R ²¹ are not bonded to each other include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, tert-butyl, n -Pentyl, tert-amyl, n-hexyl, cyclohexyl, phenyl, toluyl group and the like can be mentioned.

Examples of the hydrocarbon group when R ^{16 to} R ²¹ are bonded to each other include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.

R ^{16 to} R ²⁰ are preferably a hydrogen atom.

f represents 1 or 2, and g represents an integer of 3 to 6. That is,
(I) cyclopropyl group trisubstituted cyclotrisiloxanes in which f = 1 and g = 3,
(J) cyclopropyl group hexasubstituted cyclotrisiloxanes in which f = 2 and g = 3,
(K) cyclopropyl group tetrasubstituted cyclotetrasiloxanes in which f = 2 and g = 4,
(L) cyclopropyl group octasubstituted cyclotetrasiloxanes in which f = 2 and g = 4,
(M) cyclopropyl group pentasubstituted cyclopentasiloxane in which f = 1 and g = 5,
(N) cyclopropyl group 10-substituted cyclopentasiloxane having f = 2 and g = 5,
Or a mixture thereof.

As a specific example of the organosilane compound represented by the general formula (3),
(I) 2,4,6-tricyclopropyl-2,4,6-trimethylcyclotrisiloxane, 2,4,6-tricyclopropyl-2,4,6-triethylcyclotrisiloxane, 2,4,6 -Tricyclopropyl-2,4,6-tripropylcyclotrisiloxane, 2,4,6-tricyclopropyl-2,4,6-triisopropylcyclotrisiloxane, 2,4,6-tricyclopropyl-2 , 4,6-tributylcyclotrisiloxane, 2,4,6-tricyclopropyl-2,4,6-triisobutylcyclotrisiloxane, 2,4,6-tricyclopropyl-2,4,6-tri- sec-butylcyclotrisiloxane, 2,4,6-tricyclopropyl-2,4,6-tri-tert-butylcyclotrisiloxane, 2,4,6-trisi Ropropyl-2,4,6-tricyclobutylcyclotrisiloxane, 2,4,6-tricyclopropyl-2,4,6-tripentylcyclotrisiloxane, 2,4,6-tricyclopropyl-2,4 , 6-triisopentylcyclotrisiloxane and the like.

  2,4,6-tricyclopropyl-2,4,6-trineopentylcyclotrisiloxane, 2,4,6-tricyclopropyl-2,4,6-tri-1-methylbutylcyclotrisiloxane 2,4,6-tricyclopropyl-2,4,6-tri-2-methylbutylcyclotrisiloxane, 2,4,6-tricyclopropyl-2,4,6-tri-2,3-dimethyl Propylcyclotrisiloxane, 2,4,6-tricyclopropyl-2,4,6-trihexylcyclotrisiloxane, 2,4,6-tricyclopropyl-2,4,6-tri-1-methylpentylcyclo Trisiloxane, 2,4,6-tricyclopropyl-2,4,6-tri-2-methylpentylcyclotrisiloxane, 2,4,6-tricyclopropyl-2,4,6-tri 3-methylpentylcyclotrisiloxane, 2,4,6-tricyclopropyl-2,4,6-tri-4-methylpentylcyclotrisiloxane, 2,4,6-tricyclopropyl-2,4,6- Examples thereof include tri-1,2-dimethylbutylcyclotrisiloxane.

  2,4,6-tricyclopropyl-2,4,6-tri-1,3-dimethylbutylcyclotrisiloxane, 2,4,6-tricyclopropyl-2,4,6-tri-2, 3-dimethylbutylcyclotrisiloxane, 2,4,6-tricyclopropyl-2,4,6-tri-2,2-dimethylbutylcyclotrisiloxane, 2,4,6-tricyclopropyl-2,4 6-tri-3,3-dimethylbutylcyclotrisiloxane, 2,4,6-tricyclopropyl-2,4,6-tricyclohexylcyclotrisiloxane, 2,4,6-tricyclopropyl-2,4 6-trivinylcyclotrisiloxane, 2,4,6-tricyclopropyl-2,4,6-triallylcyclotrisiloxane, 2,4,6-tricyclopropyl-2,4,6-tri Tali Le cyclotrisiloxane, 2,4,6-cyclopropyl-2,4,6-methylidene cyclotrisiloxane and the like.

  2,4,6-tri-2-methyl-cyclopropyl-2,4,6-trimethylcyclotrisiloxane, 2,4,6-tri-2-methyl-cyclopropyl-2,4,6-triethyl Cyclotrisiloxane, 2,4,6-tri-2-methyl-cyclopropyl-2,4,6-tripropylcyclotrisiloxane, 2,4,6-tri-2-methyl-cyclopropyl-2,4 6-triisopropylcyclotrisiloxane, 2,4,6-tri-2-methyl-cyclopropyl-2,4,6-trivinylcyclotrisiloxane, 2,4,6-tri-2-methyl-cyclopropyl- 2,4,6-triallylcyclotrisiloxane, 2,4,6-tri-2-methyl-cyclopropyl-2,4,6-trimethallylcyclotrisiloxane, 2,4,6-tri-2 Methyl-cyclopropyl-2,4,6-trimethylidenecyclotrisiloxane, 2,4,6-tri-2-ethyl-cyclopropyl-2,4,6-trimethylcyclotrisiloxane, 2,4,6-tri -2-ethyl-cyclopropyl-2,4,6-triethylcyclotrisiloxane and the like.

  2,4,6-tri-2-ethyl-cyclopropyl-2,4,6-tripropylcyclotrisiloxane, 2,4,6-tri-2-ethyl-cyclopropyl-2,4,6- Triisopropylcyclotrisiloxane, 2,4,6-tri-2-ethyl-cyclopropyl-2,4,6-trivinylcyclotrisiloxane, 2,4,6-tri-2-ethyl-cyclopropyl-2, 4,6-triallylcyclotrisiloxane, 2,4,6-tri-2-ethyl-cyclopropyl-2,4,6-trimethallylcyclotrisiloxane, 2,4,6-tri-2-ethyl-cyclo Propyl-2,4,6-trimethylidenecyclotrisiloxane, 2,4,6-tri-2-propyl-cyclopropyl-2,4,6-trimethylcyclotrisiloxane, 2,4,6-to 2-propyl - cyclopropyl-2,4,6-triethyl cyclotrisiloxane, 2,4,6-2-propyl - cyclopropyl-2,4,6-tripropyl cyclotrisiloxane and the like.

  2,4,6-tri-2-propyl-cyclopropyl-2,4,6-triisopropylcyclotrisiloxane, 2,4,6-tri-2-propyl-cyclopropyl-2,4,6- Trivinylcyclotrisiloxane, 2,4,6-tri-2-propyl-cyclopropyl-2,4,6-triallylcyclotrisiloxane, 2,4,6-tri-2-propyl-cyclopropyl-2, 4,6-trimethallylcyclotrisiloxane, 2,4,6-tri-2-propyl-cyclopropyl-2,4,6-trimethylidenecyclotrisiloxane, 2,4,6-tri-2,2-methyl Ethyl-cyclopropyl-2,4,6-trimethylcyclotrisiloxane, 2,4,6-tri-2,2-methyl, ethyl-cyclopropyl-2,4,6-triethylcyclo Risiloxane, 2,4,6-tri-2,2-methyl, ethyl-cyclopropyl-2,4,6-tripropylcyclotrisiloxane, 2,4,6-tri-2,2-methyl, etc. It is done.

  Also, ethyl-cyclopropyl-2,4,6-triisopropylcyclotrisiloxane, 2,4,6-tri-2,2-methyl, ethyl-cyclopropyl-2,4,6-trivinylcyclotrisiloxane, 2,4,6-tri-2,2-methyl, ethyl-cyclopropyl-2,4,6-triallylcyclotrisiloxane, 2,4,6-tri-2,2-methyl, ethyl-cyclopropyl- 2,4,6-trimethallylcyclotrisiloxane, 2,4,6-tri-2,2-methyl, ethyl-cyclopropyl-2,4,6-trimethylidenecyclotrisiloxane, 2,4,6- Tri-1,2-dimethyl-cyclopropyl-2,4,6-trimethylcyclotrisiloxane, 2,4,6-tri-1,2-dimethyl-cyclopropyl-2,4,6-triethyl Clotrisiloxane, 2,4,6-tri-1,2-dimethyl-cyclopropyl-2,4,6-tripropylcyclotrisiloxane, 2,4,6-tri-1,2-dimethyl-cyclopropyl-2 4,6-triisopropylcyclotrisiloxane and the like.

  2,4,6-tri-1,2-dimethyl-cyclopropyl-2,4,6-trivinylcyclotrisiloxane, 2,4,6-tri-1,2-dimethyl-cyclopropyl-2, 4,6-triallylcyclotrisiloxane, 2,4,6-tri-1,2-dimethyl-cyclopropyl-2,4,6-trimethallylcyclotrisiloxane, 2,4,6-tri-1,2 -Dimethyl-cyclopropyl-2,4,6-trimethylidenecyclotrisiloxane, 2,4,6-tri-2,3-dimethyl-cyclopropyl-2,4,6-trimethylcyclotrisiloxane, 2,4, 6-tri-2,3-dimethyl-cyclopropyl-2,4,6-triethylcyclotrisiloxane, 2,4,6-tri-2,3-dimethyl-cyclopropyl-2,4,6-tripropylsilane Rotrisiloxane, 2,4,6-tri-2,3-dimethyl-cyclopropyl-2,4,6-triisopropylcyclotrisiloxane, 2,4,6-tri-2,3-dimethyl-cyclopropyl-2 , 4,6-trivinylcyclotrisiloxane, 2,4,6-tri-2,3-dimethyl-cyclopropyl-2,4,6-triallylcyclotrisiloxane, 2,4,6-tri-2, 3-dimethyl-cyclopropyl-2,4,6-trimethallylcyclotrisiloxane, 2,4,6-tri-2,3-dimethyl-cyclopropyl-2,4,6-trimethylidenecyclotrisiloxane It is done.

  (J) 2,2,4,4,6,6-hexacyclopropylcyclotrisiloxane, 2,2,4,4,6,6-hex-2-methyl-cyclopropylcyclotrisiloxane, 2,2, 4,4,6,6-hex-2-ethyl-cyclopropylcyclotrisiloxane, 2,2,4,4,6,6-hex-2-propyl-cyclopropylcyclotrisiloxane, 2,2,4, 4,6,6-hexa-2,2-methyl, ethyl-cyclopropylcyclotrisiloxane, 2,2,4,4,6,6-hexa-1,2-dimethyl-cyclopropylcyclotrisiloxane, 2, 2,4,4,6,6-hexa2,3-dimethyl-cyclopropylcyclotrisiloxane and the like.

  (K) 2,4,6,8-tetracyclopropyl-2,4,6,8-tetramethylcyclotetrasiloxane, 2,4,6,8-tetracyclopropyl-2,4,6,8-tetraethyl Cyclotetrasiloxane, 2,4,6,8-tetracyclopropyl-2,4,6,8-tetrapropylcyclotetrasiloxane, 2,4,6,8-tetracyclopropyl-2,4,6,8- Tetraisopropylcyclotetrasiloxane, 2,4,6,8-tetracyclopropyl-2,4,6,8-tetrabutylcyclotetrasiloxane, 2,4,6,8-tetracyclopropyl-2,4,6, 8-tetraisobutylcyclotetrasiloxane, 2,4,6,8-tetracyclopropyl-2,4,6,8-tetrasec-butylcyclotetrasiloxane, 2,4,6 8-tetracyclopropyl-2,4,6,8-tetratert-butylcyclotetrasiloxane, 2,4,6,8-tetracyclopropyl-2,4,6,8-tetracyclobutylcyclotetrasiloxane, etc. can give.

  2,4,6,8-tetracyclopropyl-2,4,6,8-tetrapentylcyclotetrasiloxane, 2,4,6,8-tetracyclopropyl-2,4,6,8-tetraiso Pentylcyclotetrasiloxane, 2,4,6,8-tetracyclopropyl-2,4,6,8-tetraneopentylcyclotetrasiloxane, 2,4,6,8-tetracyclopropyl-2,4,6 8-tetra1-methylbutylcyclotetrasiloxane, 2,4,6,8-tetracyclopropyl-2,4,6,8-tetra2-methylbutylcyclotetrasiloxane, 2,4,6,8-tetracyclo Propyl-2,4,6,8-tetra-2,3-dimethylpropylcyclotetrasiloxane, 2,4,6,8-tetracyclopropyl-2,4,6,8-tetrahexyl Clotetrasiloxane, 2,4,6,8-tetracyclopropyl-2,4,6,8-tetra1-methylpentylcyclotetrasiloxane, 2,4,6,8-tetracyclopropyl-2,4,6 , 8-tetra-2-methylpentylcyclotetrasiloxane and the like.

  2,4,6,8-tetracyclopropyl-2,4,6,8-tetra3-methylpentylcyclotetrasiloxane, 2,4,6,8-tetracyclopropyl-2,4,6,8 -Tetra-4-methylpentylcyclotetrasiloxane, 2,4,6,8-tetracyclopropyl-2,4,6,8-tetra-1,3-dimethylbutylcyclotetrasiloxane, 2,4,6,8-tetra Cyclopropyl-2,4,6,8-tetra-2,3-dimethylbutylcyclotetrasiloxane, 2,4,6,8-tetracyclopropyl-2,4,6,8-tetra2,2-dimethylbutylcyclo Tetrasiloxane, 2,4,6,8-tetracyclopropyl-2,4,6,8-tetra3,3-dimethylbutylcyclotetrasiloxane, 2,4,6,8-tetracyclopropyl 2,4,6,8-tetracyclohexylcyclotetrasiloxane, 2,4,6,8-tetracyclopropyl-2,4,6,8-tetravinylcyclotetrasiloxane, 2,4,6,8- Tetracyclopropyl-2,4,6,8-tetraallylcyclotetrasiloxane, 2,4,6,8-tetracyclopropyl-2,4,6,8-tetramethallylcyclotetrasiloxane, 2,4,6 , 8-tetracyclopropyl-2,4,6,8-tetramethylidenecyclotetrasiloxane and the like.

  2,4,6,8-tetra-2-methyl-cyclopropyl-2,4,6,8-tetramethylcyclotetrasiloxane, 2,4,6,8-tetra-2-methyl-cyclopropyl- 2,4,6,8-tetraethylcyclotetrasiloxane, 2,4,6,8-tetra-2-methyl-cyclopropyl-2,4,6,8-tetrapropylcyclotetrasiloxane, 2,4,6, 8-tetra-2-methyl-cyclopropyl-2,4,6,8-tetraisopropylcyclotetrasiloxane, 2,4,6,8-tetra-2-methyl-cyclopropyl-2,4,6,8- Tetravinylcyclotetrasiloxane, 2,4,6,8-tetra-2-methyl-cyclopropyl-2,4,6,8-tetraallylcyclotetrasiloxane, 2,4,6,8-tetra-2- Tyl-cyclopropyl-2,4,6,8-tetramethallylcyclotetrasiloxane, 2,4,6,8-tetra-2-methyl-cyclopropyl-2,4,6,8-tetramethylidenecyclotetra Examples thereof include siloxane.

  2,4,6,8-tetra-2-ethyl-cyclopropyl-2,4,6,8-tetramethylcyclotetrasiloxane, 2,4,6,8-tetra-2-ethyl-cyclopropyl- 2,4,6,8-tetraethylcyclotetrasiloxane, 2,4,6,8-tetra-2-ethyl-cyclopropyl-2,4,6,8-tetrapropylcyclotetrasiloxane, 2,4,6, 8-tetra-2-ethyl-cyclopropyl-2,4,6,8-tetraisopropylcyclotetrasiloxane, 2,4,6,8-tetra-2-ethyl-cyclopropyl-2,4,6,8- Tetravinylcyclotetrasiloxane, 2,4,6,8-tetra-2-ethyl-cyclopropyl-2,4,6,8-tetraallylcyclotetrasiloxane, 2,4,6,8-tetra-2- Tyl-cyclopropyl-2,4,6,8-tetramethallylcyclotetrasiloxane, 2,4,6,8-tetra-2-ethyl-cyclopropyl-2,4,6,8-tetramethylidenecyclotetra Examples thereof include siloxane.

  2,4,6,8-tetra-2-propyl-cyclopropyl-2,4,6,8-tetramethylcyclotetrasiloxane, 2,4,6,8-tetra-2-propyl-cyclopropyl- 2,4,6,8-tetraethylcyclotetrasiloxane, 2,4,6,8-tetra-2-propyl-cyclopropyl-2,4,6,8-tetrapropylcyclotetrasiloxane, 2,4,6, 8-tetra-2-propyl-cyclopropyl-2,4,6,8-tetraisopropylcyclotetrasiloxane, 2,4,6,8-tetra-2-propyl-cyclopropyl-2,4,6,8- Tetravinylcyclotetrasiloxane, 2,4,6,8-tetra-2-propyl-cyclopropyl-2,4,6,8-tetraallylcyclotetrasiloxane, 2,4,6,8- Tra-2-propyl-cyclopropyl-2,4,6,8-tetramethallylcyclotetrasiloxane, 2,4,6,8-tetra-2-propyl-cyclopropyl-2,4,6,8-tetra And methylidenecyclotetrasiloxane.

  2,4,6,8-tetra-2,2-methyl, ethyl-cyclopropyl-2,4,6,8-tetramethylcyclotetrasiloxane, 2,4,6,8-tetra-2,2 -Methyl, ethyl-cyclopropyl-2,4,6,8-tetraethylcyclotetrasiloxane, 2,4,6,8-tetra-2,2-methyl, ethyl-cyclopropyl-2,4,6,8- Tetrapropylcyclotetrasiloxane, 2,4,6,8-tetra-2,2-methyl, ethyl-cyclopropyl-2,4,6,8-tetraisopropylcyclotetrasiloxane, 2,4,6,8-tetra -2,2-methyl, ethyl-cyclopropyl-2,4,6,8-tetravinylcyclotetrasiloxane, 2,4,6,8-tetra-2,2-methyl, ethyl-cyclopropyl-2,4 , , 8-tetraallylcyclotetrasiloxane, 2,4,6,8-tetra-2,2-methyl, ethyl-cyclopropyl-2,4,6,8-tetramethallylcyclotetrasiloxane, 2,4,6 , 8-tetra-2,2-methyl and the like.

  Further, ethyl-cyclopropyl-2,4,6,8-tetramethylidenecyclotetrasiloxane, 2,4,6,8-tetra-1,2-dimethyl-cyclopropyl-2,4,6,8-tetra Methylcyclotetrasiloxane, 2,4,6,8-tetra-1,2-dimethyl-cyclopropyl-2,4,6,8-tetraethylcyclotetrasiloxane, 2,4,6,8-tetra-1,2 -Dimethyl-cyclopropyl-2,4,6,8-tetrapropylcyclotetrasiloxane, 2,4,6,8-tetra-1,2-dimethyl-cyclopropyl-2,4,6,8-tetraisopropylcyclo Tetrasiloxane, 2,4,6,8-tetra-1,2-dimethyl-cyclopropyl-2,4,6,8-tetravinyllcyclotetrasiloxane, 2,4,6,8-teto -1,2-dimethyl-cyclopropyl-2,4,6,8-tetraallylcyclotetrasiloxane, 2,4,6,8-tetra-1,2-dimethyl-cyclopropyl-2,4,6,8 -Tetramethallylcyclotetrasiloxane and the like.

  2,4,6,8-tetra-1,2-dimethyl-cyclopropyl-2,4,6,8-tetramethylidenecyclotetrasiloxane, 2,4,6,8-tetra-2,3- Dimethyl-cyclopropyl-2,4,6,8-tetramethylcyclotetrasiloxane, 2,4,6,8-tetra-2,3-dimethyl-cyclopropyl-2,4,6,8-tetraethylcyclotetrasiloxane 2,4,6,8-tetra-2,3-dimethyl-cyclopropyl-2,4,6,8-tetrapropylcyclotetrasiloxane, 2,4,6,8-tetra-2,3-dimethyl- Cyclopropyl-2,4,6,8-tetraisopropylcyclotetrasiloxane, 2,4,6,8-tetra-2,3-dimethyl-cyclopropyl-2,4,6,8-tetravinylcyclotetra Loxane, 2,4,6,8-tetra-2,3-dimethyl-cyclopropyl-2,4,6,8-tetraallylcyclotetrasiloxane, 2,4,6,8-tetra-2,3-dimethyl Cyclopropyl-2,4,6,8-tetramethallylcyclotetrasiloxane, 2,4,6,8-tetra-2,3-dimethyl-cyclopropyl-2,4,6,8-tetramethylidenecyclo Examples include tetrasiloxane.

  (L) 2,2,4,4,6,6,8,8-octacyclopropylcyclotetrasiloxane, 2,2,4,4,6,6,8,8-oct-2-methyl-cyclopropyl Cyclotetrasiloxane, 2,2,4,4,6,6,8,8-oct-2-ethyl-cyclopropylcyclotetrasiloxane, 2,2,4,4,6,6,8,8-octa- 2-propyl-cyclopropylcyclotetrasiloxane, 2,2,4,4,6,6,8,8-octa-2,2-methyl, ethyl-cyclopropylcyclotetrasiloxane, 2,2,4,4 6,6,8,8-octa-1,2-dimethyl-cyclopropylcyclotetrasiloxane, 2,2,4,4,6,6,8,8-octa-2,3-dimethyl-cyclopropylcyclotetrasiloxane Examples thereof include siloxane.

  (M) 2,4,6,8,10-pentacyclopropyl-2,4,6,8,10-tetramethylcyclopentasiloxane, 2,4,6,8,10-pentacyclopropyl-2,4 , 6,8,10-tetraethylcyclopentasiloxane, 2,4,6,8,10-pentacyclopropyl-2,4,6,8,10-tetrapropylcyclopentasiloxane, 2,4,6,8, 10-pentacyclopropyl-2,4,6,8,10-tetraisopropylcyclopentasiloxane, 2,4,6,8,10-pentacyclopropyl-2,4,6,8,10-tetrabutylcyclopenta Siloxane, 2,4,6,8,10-pentacyclopropyl-2,4,6,8,10-tetraisobutylcyclopentasiloxane, 2,4,6,8,10-pentacyclopropyl Pill-2,4,6,8,10-tetrasec-butylcyclopentasiloxane, 2,4,6,8,10-pentacyclopropyl-2,4,6,8,10-tetratert-butylcyclopenta Examples thereof include siloxane.

  2,4,6,8,10-pentacyclopropyl-2,4,6,8,10-tetracyclobutylcyclopentasiloxane, 2,4,6,8,10-pentacyclopropyl-2,4 , 6,8,10-tetrapentylcyclopentasiloxane, 2,4,6,8,10-pentacyclopropyl-2,4,6,8,10-tetraisopentylcyclopentasiloxane, 2,4,6, 8,10-pentacyclopropyl-2,4,6,8,10-tetraneopentylcyclopentasiloxane, 2,4,6,8,10-pentacyclopropyl-2,4,6,8,10-tetra 1-methylbutylcyclopentasiloxane, 2,4,6,8,10-pentacyclopropyl-2,4,6,8,10-tetra-2-methylbutylcyclopentasiloxane, 2,4, , 8,10-Pentacyclopropyl-2,4,6,8,10-tetra-2,3-dimethylpropylcyclopentasiloxane, 2,4,6,8,10-pentacyclopropyl-2,4,6, Examples include 8,10-tetrahexylcyclopentasiloxane.

  2,4,6,8,10-pentacyclopropyl-2,4,6,8,10-tetra 1-methylpentylcyclopentasiloxane, 2,4,6,8,10-pentacyclopropyl-2 , 4,6,8,10-tetra2-methylpentylcyclopentasiloxane, 2,4,6,8,10-pentacyclopropyl-2,4,6,8,10-tetra3-methylpentylcyclopentasiloxane 2,4,6,8,10-pentacyclopropyl-2,4,6,8,10-tetra4-methylpentylcyclopentasiloxane, 2,4,6,8,10-pentacyclopropyl-2, 4,6,8,10-tetra-1,2-dimethylbutylcyclopentasiloxane, 2,4,6,8,10-pentacyclopropyl-2,4,6,8,10-tetra-1,3-dimethyl Butyl cyclopentasiloxane, 2,4,6,8,10 penta cyclopropyl -2,4,6,8,10- tetra 2,3-dimethylbutyl cyclopentasiloxane and the like.

  2,4,6,8,10-pentacyclopropyl-2,4,6,8,10-tetra-2,2-dimethylbutylcyclopentasiloxane, 2,4,6,8,10-pentacyclopropyl -2,4,6,8,10-tetra-3,3-dimethylbutylcyclopentasiloxane, 2,4,6,8,10-pentacyclopropyl-2,4,6,8,10-tetracyclohexylcyclopenta Siloxane, 2,4,6,8,10-pentacyclopropyl-2,4,6,8,10-tetravinylcyclopentasiloxane, 2,4,6,8,10-pentacyclopropyl-2,4 6,8,10-tetraallylcyclopentasiloxane, 2,4,6,8,10-pentacyclopropyl-2,4,6,8,10-tetramethallylcyclopentasiloxane, 2,4 6,8,10- penta cyclopropyl -2,4,6,8,10- tetra methylidene cyclopentasiloxane and the like.

  2,4,6,8,10-penta-2-methyl-cyclopropyl-2,4,6,8,10-tetramethylcyclopentasiloxane, 2,4,6,8,10-pent-2- Methyl-cyclopropyl-2,4,6,8,10-tetraethylcyclopentasiloxane, 2,4,6,8,10-pent-2-methyl-cyclopropyl-2,4,6,8,10-tetra Propylcyclopentasiloxane, 2,4,6,8,10-pent-2-methyl-cyclopropyl-2,4,6,8,10-tetraisopropylcyclopentasiloxane, 2,4,6,8,10- Penta-2-methyl-cyclopropyl-2,4,6,8,10-tetravinylcyclopentasiloxane, 2,4,6,8,10-pent-2-methyl-cyclopropyl-2,4,6, 8, 0 tetraallyl cyclopentasiloxane, 2,4,6,8,10 pent-2-methyl - cyclopropyl -2,4,6,8,10- tetra methallyl cyclopentasiloxane and the like.

  2,4,6,8,10-penta-2-methyl-cyclopropyl-2,4,6,8,10-tetramethylidenecyclopentasiloxane, 2,4,6,8,10-penta- 2-ethyl-cyclopropyl-2,4,6,8,10-tetramethylcyclopentasiloxane, 2,4,6,8,10-pent-2-ethyl-cyclopropyl-2,4,6,8, 10-tetraethylcyclopentasiloxane, 2,4,6,8,10-pent-2-ethyl-cyclopropyl-2,4,6,8,10-tetrapropylcyclopentasiloxane, 2,4,6,8, 10-pent-2-ethyl-cyclopropyl-2,4,6,8,10-tetraisopropylcyclopentasiloxane, 2,4,6,8,10-pent-2-ethyl-cyclopropyl-2,4 6 8,10 tetravinyl cyclopentasiloxane, 2,4,6,8,10 pent-2-ethyl - cyclopropyl -2,4,6,8,10- tetraallyl cyclopentasiloxane and the like.

  2,4,6,8,10-pent-2-ethyl-cyclopropyl-2,4,6,8,10-tetramethallylcyclopentasiloxane, 2,4,6,8,10-penta- 2-ethyl-cyclopropyl-2,4,6,8,10-tetramethylidenecyclopentasiloxane, 2,4,6,8,10-pent-2-propyl-cyclopropyl-2,4,6,8 , 10-tetramethylcyclopentasiloxane, 2,4,6,8,10-pent-2-propyl-cyclopropyl-2,4,6,8,10-tetraethylcyclopentasiloxane, 2,4,6,8 , 10-pent-2-propyl-cyclopropyl-2,4,6,8,10-tetrapropylcyclopentasiloxane, 2,4,6,8,10-pent-2-propyl-cyclopropyl-2,4 Examples include 6,8,10-tetraisopropylcyclopentasiloxane, 2,4,6,8,10-pent-2-propyl-cyclopropyl-2,4,6,8,10-tetravinylcyclopentasiloxane. .

  2,4,6,8,10-penta-2-propyl-cyclopropyl-2,4,6,8,10-tetraallylcyclopentasiloxane, 2,4,6,8,10-penta-2 -Propyl-cyclopropyl-2,4,6,8,10-tetramethallylcyclopentasiloxane, 2,4,6,8,10-pent-2-propyl-cyclopropyl-2,4,6,8, 10-tetramethylidenecyclopentasiloxane, 2,4,6,8,10-penta-2,2-methyl, ethyl-cyclopropyl-2,4,6,8,10-tetramethylcyclopentasiloxane, 2, 4,6,8,10-penta-2,2-methyl, ethyl-cyclopropyl-2,4,6,8,10-tetraethylcyclopentasiloxane, 2,4,6,8,10-penta-2, 2-methyl Ethyl-cyclopropyl-2,4,6,8,10-tetrapropylcyclopentasiloxane, 2,4,6,8,10-penta-2,2-methyl, ethyl-cyclopropyl-2,4,6 Examples include 8,10-tetraisopropylcyclopentasiloxane.

  2,4,6,8,10-penta-2,2-methyl, ethyl-cyclopropyl-2,4,6,8,10-tetravinylcyclopentasiloxane, 2,4,6,8,10 -Penta-2,2-methyl, ethyl-cyclopropyl-2,4,6,8,10-tetraallylcyclopentasiloxane, 2,4,6,8,10-penta-2,2-methyl, ethyl- Cyclopropyl-2,4,6,8,10-tetramethallylcyclopentasiloxane, 2,4,6,8,10-penta-2,2-methyl, ethyl-cyclopropyl-2,4,6,8 , 10-tetramethylidenecyclopentasiloxane, 2,4,6,8,10-penta-1,2-dimethyl-cyclopropyl-2,4,6,8,10-tetramethylcyclopentasiloxane, 2,4 , 6,8,10 Penta-1,2-dimethyl-cyclopropyl-2,4,6,8,10-tetraethylcyclopentasiloxane, 2,4,6,8,10-penta-1,2-dimethyl-cyclopropyl-2,4 6,8,10-tetrapropylcyclopentasiloxane and the like.

  2,4,6,8,10-penta-1,2-dimethyl-cyclopropyl-2,4,6,8,10-tetraisopropylcyclopentasiloxane, 2,4,6,8,10-penta -1,2-dimethyl-cyclopropyl-2,4,6,8,10-tetravinylcyclopentasiloxane, 2,4,6,8,10-penta-1,2-dimethyl-cyclopropyl-2,4 , 6,8,10-tetraallylcyclopentasiloxane, 2,4,6,8,10-penta-1,2-dimethyl-cyclopropyl-2,4,6,8,10-tetramethallylcyclopentasiloxane 2,4,6,8,10-penta-1,2-dimethyl-cyclopropyl-2,4,6,8,10-tetramethylidenecyclopentasiloxane, 2,4,6,8,10-penta -2,3- Methyl-cyclopropyl-2,4,6,8,10-tetramethylcyclopentasiloxane, 2,4,6,8,10-penta-2,3-dimethyl-cyclopropyl-2,4,6,8, Examples thereof include 10-tetraethylcyclopentasiloxane.

  2,4,6,8,10-penta-2,3-dimethyl-cyclopropyl-2,4,6,8,10-tetrapropylcyclopentasiloxane, 2,4,6,8,10-penta -2,3-dimethyl-cyclopropyl-2,4,6,8,10-tetraisopropylcyclopentasiloxane, 2,4,6,8,10-penta-2,3-dimethyl-cyclopropyl-2,4 , 6,8,10-tetravinylcyclopentasiloxane, 2,4,6,8,10-penta-2,3-dimethyl-cyclopropyl-2,4,6,8,10-tetraallylcyclopentasiloxane, 2,4,6,8,10-penta-2,3-dimethyl-cyclopropyl-2,4,6,8,10-tetramethallylcyclopentasiloxane, 2,4,6,8,10-penta- 2,3-di Chill - cyclopropyl -2,4,6,8,10- tetra methylidene cyclopentasiloxane and the like.

  (N) 2,2,4,4,6,6,8,8,10,10-decacyclopropylcyclopentasiloxane, 2,2,4,4,6,6,8,8,10,10- Deca-2-methyl-cyclopropylcyclopentasiloxane, 2,2,4,4,6,6,8,8,10,10-dec-2-ethyl-cyclopropylcyclopentasiloxane, 2,2,4, 4,6,6,8,8,10,10-dec-2-propyl-cyclopropylcyclopentasiloxane, 2,2,4,4,6,6,8,8,10,10-dec-2, 2-methyl, ethyl-cyclopropylcyclopentasiloxane, 2,2,4,4,6,6,8,8,10,10-deca-1,2-dimethyl-cyclopropylcyclopentasiloxane, 2,2, 4, 4, 6, 6, 8, 8, 10, 10-deca-2, - dimethyl - cyclopropyl cyclopentasiloxane and the like.

  Among them, 2,4,6-tricyclopropyl-2,4,6-trimethylcyclotrisiloxane, 2,2,4,4,6,6-hexacyclopropylcyclotrisiloxane, 2,4,6,8-tetra Cyclopropyl-2,4,6,8-tetramethylcyclotetrasiloxane or 2,2,4,4,6,6,8,8-octacyclopropylcyclotetrasiloxane is particularly preferred.

  The method for producing the organosilane compound represented by the general formula (3) is not particularly limited. For example, a cyclopropyl group trisubstituted six-membered siloxane in which f = 1 and g = 3 is The organic silane compound represented by the general formula (7) where f = 1 can be produced by polycondensation in the presence of water and an acid.

  By adopting this production method, production of by-products is suppressed, and an organic silane compound represented by the general formula (3) having a high purity can be obtained in a high yield.

  Regarding the purification method of the organic silane compound represented by the general formula (3), the moisture content useful for use as an insulating film material is less than 50 ppm, and the contents of elements other than silicon, carbon, oxygen, and hydrogen are set. In order to make it less than 10 ppb, it may be removed by means such as filtration using a glass filter, sintered porous body, etc., distillation at atmospheric pressure or reduced pressure, or column separation purification using silica, alumina or polymer gel. At this time, these means may be used in combination as necessary.

  In the production, the method in the organometallic compound synthesis field is followed. That is, the dehydration and deoxygenation is performed in a nitrogen or argon atmosphere, and the solvent to be used and the column filler for purification are preferably subjected to dehydration operations in advance. It is also preferable to remove impurities such as metal residues and particles.

  When the Si-containing film forming material of the present invention is used as a material for an insulating film, it is particularly preferable that the content of elements other than silicon, carbon, oxygen, and hydrogen is less than 10 ppb and the water content is less than 50 ppm. .

  A Si-containing film can be produced using the Si-containing film-forming material of the present invention. The film formation method at this time is not limited, but is preferably performed by CVD, and particularly preferably by PECVD.

  At this time, the type of PECVD and the apparatus to be used are not particularly limited. For example, the PECVD used is generally used in the technical field such as the semiconductor manufacturing field and the liquid crystal display manufacturing field.

  In the PECVD apparatus, the Si-containing film forming material of the present invention is vaporized by a vaporizer, introduced into a film forming chamber, applied to an electrode in the film forming chamber by a high frequency power source, and plasma is generated to form a film forming chamber. A PECVD thin film can be formed on the inner silicon substrate or the like. At this time, a gas such as argon or helium, or an oxidant such as oxygen or nitrous oxide may be introduced for the purpose of generating plasma. Further, for the purpose of making the thin film porous, an organic peroxide or an epoxy compound may be introduced simultaneously. When a film is formed using the Si-containing film forming material of the present invention by a PECVD apparatus, a thin film suitable as a low dielectric constant material (Low-k material) for semiconductor devices can be formed.

  The plasma generation method of the PECVD apparatus is not particularly limited, and inductively coupled plasma, capacitively coupled plasma, ECR plasma, or the like used in the art can be used. Inductively coupled plasma and capacitively coupled plasma are preferable. As the plasma generation source, various types such as a parallel plate type and an antenna type can be used. As the inert gas supplied to the chamber of the PECVD apparatus, helium, argon, krypton, neon used in the technical field. Xenon, etc. can be used.

  Although a Si-containing film is obtained in this way, this film has a low relative dielectric constant, and depending on conditions, a film having a relative dielectric constant of 2.0 or less can be obtained. Therefore, it can be used as a low dielectric constant film. it can. Further, this film preferably has a cyclic siloxane structure. In particular, when a film is formed using the compound represented by the general formula (3), the cyclic siloxane structure in the film may be the one in which the cyclic siloxane structure in the compound represented by the general formula (3) remains. Also, it may be newly generated by plasma. As a result, the film having a cyclic siloxane structure is a porous film having a main pore diameter of 1 nm or less, and the pores are not continuous, there is no metal diffusion into the film, and high mechanical properties are obtained. Since it has high heat conductivity, it is a thin film particularly suitable as a low dielectric constant material (low-k material) for semiconductor devices. Therefore, it is preferable to form a film under PECVD conditions that do not destroy the cyclic siloxane structure in the cyclic siloxane compound represented by the general formula (3).

  As an example of the PECVD apparatus, FIG. 1 shows a parallel plate capacitively coupled PECVD apparatus. A parallel plate capacitive coupling type PECVD apparatus 1 shown in FIG. 1 has a showerhead upper electrode, a lower electrode capable of controlling the temperature of the substrate, and a Si-containing film forming material of the present invention (hereinafter abbreviated as a precursor) in a PECVD apparatus chamber. It consists of a vaporizer device for vaporizing, a plasma generator comprising a high-frequency power source and a matching circuit, and an exhaust system comprising a vacuum pump.

  Specifically, this PECVD apparatus 1 is provided with a temperature control for installing a PECVD chamber 2, an upper electrode 3 having a shower head for uniformly supplying a precursor into the chamber, and a thin film forming substrate 5 such as a Si substrate. A lower electrode 4 having a device 8, vaporizers 9 to 15 for vaporizing a precursor, a matching circuit 6 and an RF power source 7 as a plasma generation source, and an exhaust device 16 for exhausting unreacted substances and by-products in the chamber Consists of. Reference numerals 17 and 18 denote grounds.

  The matching circuit 6 and the RF power source 7 which are plasma generation sources are connected to the upper electrode 3 and generate plasma by discharge. The standard of the RF power source 7 is not particularly limited, but the power used in the technical field is 1 W to 2000 W, preferably 10 W to 1000 W, the frequency is 50 kHz to 2.5 GHz, preferably 100 kHz to 100 MHz, particularly preferably 200 kHz. An RF power source of ˜50 MHz can be used.

  The substrate temperature is not particularly limited, but is −90 to 1,000 ° C., preferably 0 ° C. to 500 ° C.

  The vaporizer is filled with a precursor 13 that is liquid at normal temperature and pressure, and is a container 12 that includes a dip pipe and a pipe 15 that is pressurized by the inert gas, and a liquid flow rate control device that controls the flow rate of the precursor 13 that is a liquid. 10. A vaporizer 9 for vaporizing a precursor 13, which is a liquid, a pipe 14 for supplying the inert gas into the PECVD apparatus chamber via the vaporizer, and a gas flow rate controller 11 for controlling the flow rate thereof. This vaporizer is connected by piping from the vaporizer 9 to the upper electrode 3 having a shower head.

  As an example of a PECVD apparatus, FIG. 2 shows an inductively coupled remote PECVD apparatus. An inductively coupled remote PECVD apparatus 19 shown in FIG. 2 includes a plasma generation unit wound in a coil shape around quartz at the upper part of a PECVD apparatus chamber, a substrate installation unit capable of temperature control, and a vaporizer that vaporizes and supplies a precursor to the chamber. It consists of a plasma generator comprising a device, a high frequency power source and a matching circuit, and an exhaust system comprising a vacuum pump.

  Specifically, the PECVD apparatus 19 includes a PECVD chamber 20, a coil 21 that is a plasma generation unit and a quartz tube 22, a heater unit 23 for installing a thin film forming substrate 24 such as a Si substrate, and a temperature control unit 27, It comprises vaporizers 28 to 35 for vaporizing the precursor, a matching circuit 25 and an RF power source 26 as a plasma generation source, and an exhaust device 36 for exhausting unreacted substances and by-products in the chamber. 37 is a ground.

  A coil around quartz, which is a plasma generation unit, is connected to the matching circuit 25 and is discharged in the quartz tube by an antenna current magnetic field by RF current to generate plasma. Although it does not specifically limit about the specification of RF power supply 26, The electric power used in the said technical field is 1W-2000W, Preferably it is 10W-1000W, A frequency is 50 kHz-2.5 GHz, Preferably it is 100 kHz-100 MHz, Most preferably, it is 200 kHz- A 50 MHz RF power supply can be used.

  The substrate temperature is not particularly limited, but is −90 to 1,000 ° C., preferably 0 ° C. to 500 ° C.

  The vaporizer is filled with a precursor 33 that is liquid at normal temperature and pressure, a container 32 having a dip pipe and a pipe 35 that is pressurized with the inert gas, and a liquid flow rate control device that controls the flow rate of the precursor 33 that is a liquid. 29, a vaporizer 28 for vaporizing the precursor 33, which is a liquid, a pipe 34 for supplying the inert gas into the PECVD apparatus chamber via the vaporizer, a gas flow rate controller 30 for controlling the flow rate, an inert gas, It comprises a shower head 31 for uniformly supplying the gasified precursor 33 into the chamber.

  A precursor is gasified using the PECVD apparatus etc. which were illustrated above, is supplied in a chamber with an inert gas as needed, and is formed into a film by PECVD. The pressure in the chamber at this time is not particularly limited, but is 0.1 Pa to 10000 Pa, preferably 1 Pa to 5000 Pa.

  Moreover, the Si-containing film obtained by the present invention is further subjected to heat treatment, ultraviolet irradiation treatment, or electron beam treatment, whereby a porous thin film with improved mechanical strength can be obtained. You may perform the process which combined these. The thin film obtained by this treatment is suitable as a low dielectric constant insulating material.

  Any of the Si-containing films according to the present invention is suitable as a low dielectric constant material, and can be used as an insulating film in a semiconductor device. It is particularly suitable for the manufacture of ULSI using multilayer wiring.

  Further, 2,4,6-tricyclopropyl-2,4,6-trimethylcyclotrisiloxane, 2,2,4,4,6,6-hexacyclopropylcyclohexane which can be used as the Si-containing film forming material of the present invention. Trisiloxane, 2,4,6,8-tetracyclopropyl-2,4,6,8-tetramethylcyclotetrasiloxane, or 2,2,4,4,6,6,8,8-octacyclopropylcyclo Tetrasiloxane is a novel compound.

  By using the Si-containing film forming material of the present invention, a Si-containing film can be obtained, which has a low dielectric constant and high mechanical strength as a low dielectric constant material in a semiconductor device interlayer insulating film. In particular, by forming a film by PECVD using the Si-containing film forming material of the present invention, it is possible to provide a porous material that has been difficult with the conventional method, which is useful as an interphase insulating film.

It is a figure which shows a parallel plate capacitive coupling type PECVD apparatus. It is a figure which shows an inductively coupled remote PECVD apparatus.

  Examples are shown below, but the present invention is not limited to these Examples.

Reference example 1
[Production of organosilane compound having a structure in which a cyclopropyl group is directly bonded to a silicon atom]
Under a nitrogen stream, a 1 l reactor equipped with a dropping funnel was charged with 29.17 g (1.2 mol) of metallic magnesium and 800 ml of dried diethyl ether, and stirred at room temperature, from the dropping funnel, bromocyclopropane 245 A mixed solution of .18 g (1.2 mol) and 62.09 g (0.4 mol) of tetramethoxysilane was added dropwise, and the mixture was further stirred for 24 hours under diethyl ether reflux conditions. After completion of the reaction, unreacted metallic magnesium and by-product MgBr (OMe) were removed by filtration to obtain a diethyl ether solution of dicyclopropyldimethoxysilane. Diethyl ether was distilled off, and dicyclopropyldimethoxysilane as the target product was separated and purified by distillation. The result was a yield of 15%. The isolated dicyclopropyldimethoxysilane was analyzed by ¹ H-NMR, ¹³ C-NMR, and GC-MS. The results were as follows, indicating that it was a high-purity target product.
[Physical properties of dicyclopropyldimethoxysilane]
_{^{1 H-NMR (CDCl 3)}} ; - 0.50~-0.48ppm (m, 2H, -CH 2 -C H -Si), 0.42~0.46ppm (m, 4H, -C H 2 - _{CH-Si), 0.56~0.62ppm (m} , 4H, -C H 2 -CH-Si), 3.56 (s, 6H, C H 3 O-Si)
_{^{13 C-NMR (CDCl 3)}} ; - 9.28ppm (-CH 2 - C H-Si), 0.21ppm (- C H 2 -CH-Si), 0.84ppm (- C H 2 -CH-Si ), 50.90 ppm ( C H ₃ O—Si)
_{GC-MS; Mw = 172,} C 8 H 16 O 2 Si.

Example 1
[Production of cyclic organosilane compound having a structure in which a cyclopropyl group is directly bonded to a silicon atom]
Under a nitrogen stream, 2.53 g (0.14 mol) of water and 1.97 g (0.02 mol) of concentrated sulfuric acid were charged into a 20 ml reactor, and 2.94 g (0.02 mol) of cyclopropylmethyldimethoxysilane was stirred at room temperature. ) And then reacted at room temperature for 1 hour and at 80 ° C. for 1 hour, and then distilled to obtain 2,4,6-tricyclopropyl-2,4,6-trimethylcyclotrisiloxane (yield 15). %) And 2,4,6,8-tetracyclopropyl-2,4,6,8-tetramethylcyclotetrasiloxane (14% yield).
[Physical properties of 2,4,6-tricyclopropyl-2,4,6-trimethylcyclotrisiloxane]
^{_{1 H-NMR (CDCl 3)}} ; - 0.40~-0.38ppm (m, 3H, -CH 2 -C H -Si), 0.138ppm (s, 9H, C H 3 -Si), 0. _{36-0.40ppm (m, 6H, -C H} 2 -CH-Si), 0.54-0.60ppm (m, 6H, -C H 2 -CH-Si)
^{_{13 C-NMR (CDCl 3)}} ; - 4.17ppm (C H 3 -Si), - 1.38ppm (-CH 2 - C H-Si), 1.18 (- C H 2 -CH-Si) ppm
_{GC-MS; Mw = 300,} C 12 H 24 O 3 Si 3.
[Physical properties of 2,4,6,8-tetracyclopropyl-2,4,6,8-tetramethylcyclotetrasiloxane]
^{_{1 H-NMR (CDCl 3)}} ; - 0.48~-0.40ppm (m, 4H, -CH 2 -C H -Si), 0.02-0.10ppm (m, 12H, C H 3 -Si _{), 2.80-0.38ppm (m, 8H,} -C H 2 -CH-Si), 0.48-0.54ppm (m, 8H, -C H 2 -CH-Si)
^{_{13 C-NMR (CDCl 3)}} ; - 4.23ppm (C H 3 -Si), - 1.34ppm (-CH 2 - C H-Si), 1.21ppm (- C H 2 -CH-Si)
_{GC-MS; Mw = 400,} C 16 H 32 O 4 Si 4.

Example 2
[Production of cyclic organosilane compound having a structure in which a cyclopropyl group is directly bonded to a silicon atom]
Under a nitrogen stream, 1.46 g (0.81 mol) of water and 1.14 g (0.01 mol) of concentrated sulfuric acid were charged into a 20 ml reactor, and 2.00 g (0.01 mol) of dicyclopropyldimethoxysilane was stirred at room temperature. ) Was added dropwise at 0 ° C., reacted at 80 ° C. for 1 hour, extracted, and distilled to obtain the desired 2,2,4,4,6,6-hexacyclopropylcyclotrisiloxane (yield 9%). ) And 2,2,4,4,6,6,8,8-octacyclopropylcyclotetrasiloxane (yield 4%).
[Properties of 2,2,4,4,6,6-hexacyclopropylcyclotrisiloxane]
^{_{1 H-NMR (CDCl 3)}} ; - 0.42~-0.36ppm (m, 6H, -CH 2 -C H -Si), 0.44-0.48ppm (m, 12H, -C H 2 - CH-Si), 0.54-0.60ppm (m , 12H, -C H 2 -CH-Si)
^{_{13 C-NMR (CDCl 3)}} ; - 5.81ppm (-CH 2 - C H-Si), 1.10ppm (- C H 2 -CH-Si)
_{GC-MS; Mw = 378,} C 18 H 30 O 3 Si 3.
[Physical properties of 2,2,4,4,6,6,8,8-octacyclopropylcyclotetrasiloxane]
_{1H-NMR (CDCl 3);} - 0.49~-0.40ppm (m, 8H, -CH 2 -C H -Si), 0.38-0.42ppm (m, 16H, -C H 2 -CH _{-Si), 0.48-0.53ppm (m, 16H} , -C H 2 -CH-Si)
_{GC-MS; Mw = 504,} C 24 H 40 O 4 Si 4.

Reference example 2
[PECVD film formation using organosilane compounds]
The dicyclopropyldimethoxysilane synthesized in Reference Example 1 was formed on a silicon substrate using the parallel plate capacitively coupled PECVD apparatus shown in FIG. The film forming conditions were as follows: argon gas as an inert gas was supplied at 10 sccm, vaporized dicyclopropyldimethoxysilane was continuously supplied so that the internal pressure of the chamber became 10 Pa, the substrate temperature was 100 ° C., the RF power source power was 30 W, the RF power source The film was formed under the condition of a frequency of 13.56 MHz. As a result, the film formation rate was 113 nm / min. Met.

Example 3 [PECVD film formation using organosilane compound represented by general formula (3)]
Similar to Reference Example 2 except that instead of dicyclopropyldimethoxysilane in Reference Example 2, 2,4,6-tricyclopropyl-2,4,6-trimethylcyclotrisiloxane synthesized in Example 1 was used. Thus, a PECVD thin film was obtained. As a result, the film formation rate was 52.0 nm / min. Met.

1. 1. Parallel plate capacitively coupled PECVD apparatus 2. PECVD chamber Upper electrode 4. Lower electrode 5. 5. Substrate for thin film formation 6. Matching circuit RF power supply8. 8. Temperature control device Vaporizer 10. Liquid flow controller 11. Gas flow control device 12. Container 13. Precursor 14. Piping 15. Piping 16. Exhaust device 17. Earth 18. Earth 19. Inductively coupled remote PECVD apparatus 20. PECVD chamber 21. Coil 22. Quartz tube 23. Heater section 24. Thin film forming substrate 25. Matching circuit 26. RF power supply 27. Temperature controller 28. Vaporizer 29. Liquid flow control device 30. Gas flow control device 31. Shower head 32. Container 33. Precursor 34. Piping 35. Piping 36. Exhaust device 37. Earth

Claims (6)

2,4,6-tricyclopropyl-2,4,6-trimethylcyclotrisiloxane, 2,2,4,4,6,6-hexacyclopropylcyclotrisiloxane, 2,4,6,8-tetracyclo Propyl-2,4,6,8-tetramethylcyclotetrasiloxane or 2,2,4,4,6,6,8,8-octacyclopropylcyclotetrasiloxane. 2,4,6-tricyclopropyl-2,4,6-trimethylcyclotrisiloxane and / or 2,4,6,8-tetra, characterized by hydrolyzing and separating and purifying cyclopropylmethyldimethoxysilane A method for producing cyclopropyl-2,4,6,8-tetramethylcyclotetrasiloxane. 2,2,4,4,6,6-hexacyclopropylcyclotrisiloxane and / or 2,2,4,4,6,6, characterized in that dicyclopropyldimethoxysilane is hydrolyzed and separated and purified , 8,8-octacyclopropylcyclotetrasiloxane production method. A Si-containing film-forming material comprising the compound according to claim 1. A method for producing a Si-containing film, wherein the Si-containing film forming material according to claim 4 is used. The manufacturing method according to claim 5, wherein the manufacturing method is performed by a chemical vapor deposition method.

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