JP2006210791A - Si-containing film-forming material and utility thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a novel Si-containing film-forming material, in particular a material for low dielectric constant insulating films which contains a siloxane compound and is suitable for PECVD apparatuses and also an Si-containing film obtained by using such a material, and a semiconductor device comprising such an Si-containing film. <P>SOLUTION: Specifically disclosed is an Si-containing film-forming material which contains a siloxane compound represented by the general formula (1) (wherein A represents a group containing at least one selected from the group consisting of an oxygen atom, a boron atom, and a nitrogen atom; R<SP>1</SP>, R<SP>2</SP>depict a hydrogen atom or a hydrocarbon group, p represents an integer of 1 to 4; q indicates an integer of 0 to 3, and (p+q) is an integer of 1 to 4). <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a Si-containing film forming material and the like, and more particularly to a low dielectric constant interlayer insulating film material used in a multilayer wiring technique in logic ULSI. In particular, the present invention relates to a Si-containing film-forming material containing a silane compound for plasma polymerization and its use.

  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, but recently, in order to obtain a more uniform interlayer insulating film, tetra 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.

  In addition, there are two methods for forming an insulating film: a coating type in which an insulating film polymer solution is applied by spin coating or the like, and a CVD method in which a film is formed mainly by plasma polymerization in a plasma CVD apparatus. .

  As a proposal of the plasma CVD method, for example, in Patent Document 1, a method of forming a trimethylsilane oxide thin film from trimethylsilane and oxygen by the plasma CVD method, and in Patent Document 2, methyl, ethyl, n-propyl, etc. There has been proposed a method for forming an alkyl oxysilane thin film by plasma CVD from an alkoxysilane having an alkynyl and aryl group such as linear alkyl and vinylphenyl. Insulating films made of these conventional plasma CVD materials have good adhesion to copper wiring materials as barrier metals and wiring materials, but the uniformity of the film is a problem, film formation speed, relative dielectric constant There were cases where the rate was insufficient.

  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 3, a coating solution obtained by hydrolytic polycondensation of 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 JP 2000-302791 A

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

  The present inventors have found that a silane compound having a substituent containing a hetero atom is suitable as an insulating film, particularly a low dielectric constant interlayer insulating film material for a semiconductor device, and has completed the present invention. .

  That is, the present invention provides the following general formula (1)

（式中、Ａは、酸素原子、ホウ素原子、及び窒素原子からなる群から選ばれた少なくとも一種を含む基を表し、Ｒ^１、Ｒ^２は、水素原子または、炭化水素基を表す。ｐは、１乃至４の整数を表し、ｑは、０乃至３の整数を表す。ｐ＋ｑは、１乃至４である。）で示されるシラン化合物を含有することを特徴とする、Ｓｉ含有膜形成材料である。

(In the formula, A represents a group containing at least one selected from the group consisting of an oxygen atom, a boron atom, and a nitrogen atom, and R ¹ and R ² represent a hydrogen atom or a hydrocarbon group. 1 represents an integer of 1 to 4, and q represents an integer of 0 to 3. p + q is 1 to 4). is there.

  Moreover, this invention is a manufacturing method of Si containing film characterized by using the above-mentioned Si containing film forming material as a raw material. Moreover, this invention is a Si containing film characterized by the above-mentioned manufacturing method. The present invention is also a method for producing a Si-containing film, characterized by subjecting the above-mentioned Si-containing film to heat treatment, ultraviolet irradiation treatment, and electron beam treatment. Moreover, this invention is a Si containing film characterized by the above-mentioned manufacturing method. Moreover, this invention is a semiconductor device characterized by using the above-mentioned Si containing film as an insulating film.

  Details of the present invention will be described below.

  In the general formula (1), A represents a group containing at least one selected from the group consisting of an oxygen atom, a boron atom, and a nitrogen atom, and has a linear, branched, or cyclic structure. It's okay.

  As A containing oxygen, for example, the following general formula (2)

（式中、Ｒ^３は、炭化水素基を表し、Ｒ^４は、炭化水素残基を表す。ｘは、Ｒ^４に置換するＯＲ^３の数であり、１以上の整数である。）で示される酸素含有基を挙げることができる。

(Wherein R ³ represents a hydrocarbon group, R ⁴ represents a hydrocarbon residue, x is the number of OR ³ substituted for R ⁴ and is an integer of 1 or more). And oxygen-containing groups.

When R ¹ , R ² , R ³ and R ⁵ and R ⁷ shown below represent a hydrocarbon group, a saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms is preferable, linear, branched, cyclic It may have any structure. Further, when x is 2 or more in the above general formula (2), or when y or z is 2 or more in the following general formula (4) or (6), they are bonded to each other to form a cyclic structure. Also good. When the number of carbon atoms exceeds 20, it may be difficult to procure the corresponding raw material such as organic halide, or even if it can be procured, the purity may be low. In consideration of stable use in a CVD apparatus, a hydrocarbon group having 1 to 6 carbon atoms is particularly preferable in that the vapor pressure of the organosilane compound does not become too low.

Examples of the hydrocarbon group of R ¹ , R ² , R ³ and R ⁵ and R ⁷ shown below are preferably those having 1 to 20 carbon atoms, more preferably alkyl groups and aryl groups having 1 to 6 carbon atoms. An arylalkyl group, an alkylaryl group, an alkenyl group, an arylalkenyl group, an alkenylaryl group, an alkynyl group, an arylalkynyl group, and an alkynylaryl group.

  Specific examples include methyl, ethyl, n-propyl, i-propyl, cyclopropyl, n-butyl, i-butyl, sec-butyl, tert. -Butyl, cyclobutyl, n-pentyl, tert. -Alkyl groups such as amyl, cyclopentyl, n-hexyl, cyclohexyl, 2-ethylhexyl, aryl groups such as phenyl, diphenyl, naphthyl, arylalkyl groups such as benzyl, methylbenzyl, o-toluyl, m-toluyl, p-toluyl 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2,4,6-trimethyl Examples thereof include alkylaryl groups such as phenyl, o-ethylphenyl, m-ethylphenyl and p-ethylphenyl.

  Also vinyl, allyl, 1-propenyl, 1-butenyl, 1,3-butadienyl, 1-pentenyl, 1-cyclopentenyl, 2-cyclopentenyl, cyclopentadienyl, methylcyclopentadienyl, ethylcyclopentadienyl, Alkenyl groups such as 1-hexenyl, 1-cyclohexenyl, 2,4-cyclohexadienyl, 2,5-cyclohexadienyl, 2,4,6-cycloheptatrienyl, 5-norbornen-2-yl, 2- Arylalkenyl groups such as phenyl-1-ethenyl, alkenylaryl groups such as o-styryl, m-styryl, p-styryl, ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-hexini , 3-hexynyl, 5-alkynyl group hexynyl, etc., 2-phenyl-1-arylalkynyl group ethynyl etc., and 2-ethynyl -2 alkynyl aryl groups such as phenyl and the like.

R ⁴ and R ⁶ and R ⁸ shown below are R ¹ , R ² , R ³ and R ⁵ and R ⁷ shown below as examples of the hydrocarbon group structure shown as x, y, or A hydrocarbon residue represented by a structure excluding z hydrogen atoms can be shown, preferably a saturated or unsaturated hydrocarbon residue having 1 to 20 carbon atoms, linear, branched, cyclic Any of these structures may be employed, and an aromatic group is more preferred. When the number of carbon atoms exceeds 20, the vapor pressure of the produced organosilane becomes low, and it may be difficult to use in the PECVD apparatus, which may be undesirable.

  As A containing nitrogen, for example, the following general formula (3)

（式中、Ｒ^５は、炭化水素残基を表す。）又は、下記一般式（４）

(Wherein R ⁵ represents a hydrocarbon residue) or the following general formula (4)

（式中、Ｒ^５は、炭化水素基を表し、Ｒ^６は、炭化水素残基を表す。ｙは、Ｒ^６に置換するＮＲ^５ _２の数であり、１以上の整数である。）で示される窒素含有基を挙げることができる。上式においてＲ^５どうしは、同一であっても異なっても良い。

(Wherein R ⁵ represents a hydrocarbon group, R ⁶ represents a hydrocarbon residue, and y represents the number of NR ⁵ ₂ substituted for R ⁶ and is an integer of 1 or more). Mention may be made of the nitrogen-containing groups shown. In the above formula, R ⁵ may be the same or different.

  As A containing boron, for example, the following general formula (5)

（式中、Ｒ^７は、炭化水素残基を表す。）又は、下記一般式（６）

(Wherein R ⁷ represents a hydrocarbon residue) or the following general formula (6)

（式中、Ｒ^７は、炭化水素基を表し、Ｒ^８は、炭化水素残基を表す。ｚは、Ｒ^８に置換するＢＲ^７ _２の数であり、１以上の整数である。）で示されるホウ素含有基を挙げることができる。上式においてＲ^７どうしは、同一であっても異なっても良い。

(Wherein R ⁷ represents a hydrocarbon group, R ⁸ represents a hydrocarbon residue, z is the number of BR ⁷ ₂ substituted for R ⁸ and is an integer of 1 or more). Mention may be made of the boron-containing groups shown. In the above formula, R ⁷ may be the same or different.

  A Si-containing film-forming material comprising the silane compound represented by the general formula (1) having a structure in which the substituents of the general formulas (2) to (6) are mixed is also included in the present invention. Enter the range.

When R ¹ is a secondary hydrocarbon group or a tertiary hydrocarbon group directly connected to an Si atom, the silane compound represented by the general formula (1) is stabilized in plasma and has a low relative dielectric constant value. Particularly preferred is a thin film having high mechanical properties. Moreover, it is preferable that the molecular weight of the silane compound represented by General formula (1) is less than 1000. This is because when the film is formed by the CVD method, a higher vapor pressure is more advantageous for vaporization.

  Specific examples of the silane compound represented by the general formula (1) include methyl (4-methoxyphenyl) dimethoxysilane, methyl (2,4-dimethoxyphenyl) dimethoxysilane, and methyl (2,5-dimethoxyphenyl) dimethoxy. Silane, methyl (3,4-dimethoxyphenyl) dimethoxysilane, methyl (3,5-dimethoxyphenyl) dimethoxysilane, methyl (2,3,4-trimethoxyphenyl) dimethoxysilane, methyl (3,4,5-tri Methoxyphenyl) dimethoxysilane, methyl (4-ethoxyphenyl) dimethoxysilane, methyl (2,5-diethoxyphenyl) dimethoxysilane, methyl (4-n-propoxyphenyl) dimethoxysilane, methyl (4-isopropoxyphenyl) dimethoxy Silane, methyl (4-n- Toxiphenyl) dimethoxysilane, methyl (4-isobutoxyphenyl) dimethoxysilane, methyl (4-tret.-butoxyphenyl) dimethoxysilane, ethyl (4-methoxyphenyl) dimethoxysilane,) ethyl (4-tret.-butoxyphenyl) ) Dimethoxysilane, vinyl (4-methoxyphenyl) dimethoxysilane, vinyl (4-tret.-butoxyphenyl) dimethoxysilane and the like.

  Also, isopropyl (4-methoxyphenyl) dimethoxysilane, isopropyl (2,4-dimethoxyphenyl) dimethoxysilane, isopropyl (2,5-dimethoxyphenyl) dimethoxysilane, isopropyl (3,4-dimethoxyphenyl) dimethoxysilane, isopropyl (3 , 5-Dimethoxyphenyl) dimethoxysilane, isopropyl (2,3,4-trimethoxyphenyl) dimethoxysilane, isopropyl (3,4,5-trimethoxyphenyl) dimethoxysilane, isopropyl (4-ethoxyphenyl) dimethoxysilane, isopropyl (2,5-diethoxyphenyl) dimethoxysilane, isopropyl (4-n-propoxyphenyl) dimethoxysilane, isopropyl (4-isopropoxyphenyl) dimethoxysilane, Propyl (4-n-butoxyphenyl) dimethoxysilane, isopropyl (4-isobutoxyphenyl) dimethoxysilane, isopropyl (4-tret.- butoxyphenyl) dimethoxysilane and the like.

  Also tert. -Butyl (4-methoxyphenyl) dimethoxysilane, tert. -Butyl (2,4-dimethoxyphenyl) dimethoxysilane, tert. -Butyl (2,5-dimethoxyphenyl) dimethoxysilane, tert. -Butyl (3,4-dimethoxyphenyl) dimethoxysilane, tert. -Butyl (3,5-dimethoxyphenyl) dimethoxysilane, tert. -Butyl (2,3,4-trimethoxyphenyl) dimethoxysilane, tert. -Butyl (3,4,5-trimethoxyphenyl) dimethoxysilane, tert. -Butyl (4-ethoxyphenyl) dimethoxysilane, tert. -Butyl (2,5-diethoxyphenyl) dimethoxysilane, tert. -Butyl (4-n-propoxyphenyl) dimethoxysilane, tert. -Butyl (4-isopropoxyphenyl) dimethoxysilane, tert. -Butyl (4-n-butoxyphenyl) dimethoxysilane, tert. -Butyl (4-isobutoxyphenyl) dimethoxysilane, tert. -Butyl (4-tret.-butoxyphenyl) dimethoxysilane and the like.

  Further, methyl (4-methoxyphenyl) diethoxysilane, methyl (4-tret.-butoxyphenyl) diethoxysilane, dimethyl (4-methoxyphenyl) methoxysilane, dimethyl (4-tret.-butoxyphenyl) methoxysilane and the like Can be mentioned.

  Also, bis (4-methoxyphenyl) dimethoxysilane, bis (4-tret.-butoxyphenyl) dimethoxysilane, bis (4-methoxyphenyl) methylmethoxysilane, bis (4-tret.-butoxyphenyl) methylmethoxysilane, bis (4-methoxyphenyl) ethylmethoxysilane, bis (4-tret.-butoxyphenyl) ethylmethoxysilane, bis (4-methoxyphenyl) vinylmethoxysilane, bis (4-tret.-butoxyphenyl) vinylmethoxysilane, bis (4-methoxyphenyl) -n-propylmethoxysilane, bis (4-tret.-butoxyphenyl) -n-propylmethoxysilane, bis (4-methoxyphenyl) isopropylmethoxysilane, bis (4-tret.-butoxyphenyl) Isopropyl silane, bis (4-methoxyphenyl)-tert.. -Butylmethoxysilane, bis (4-tret.-butoxyphenyl) -tert. -Butylmethoxysilane, bis (4-methoxyphenyl) -tert. -Butylethoxysilane, bis (4-tret.-butoxyphenyl) -tert. -Butylethoxysilane, bis (4-methoxyphenyl) sisilane, bis (4-tret.-butoxyphenyl) silane and the like.

  Further, tris (4-methoxyphenyl) methoxysilane, tris (4-tret.-butoxyphenyl) methoxysilane, tris (4-methoxyphenyl) ethoxysilane, tris (4-tret.-butoxyphenyl) ethoxysilane, tris (4 -Methoxyphenyl) silane, tris (4-tret.-butoxyphenyl) sisilane, tetrakis (4-methoxyphenyl) silane, tetrakis (4-tret.-butoxyphenyl) silane and the like.

  Also, methyl (dimethylamino) dimethoxysilane, methyl (diethylamino) dimethoxysilane, ethyl (dimethylamino) dimethoxysilane, ethyl (diethylamino) dimethoxysilane, vinyl (dimethylamino) dimethoxysilane, vinyl (diethylamino) dimethoxysilane, n-propyl ( Dimethylamino) dimethoxysilane, n-propyl (diethylamino) dimethoxysilane, isopropyl (dimethylamino) dimethoxysilane, isopropyl (diethylamino) dimethoxysilane, n-butyl (dimethylamino) dimethoxysilane, n-butyl (diethylamino) dimethoxysilane, isobutyl (Dimethylamino) dimethoxysilane, isobutyl (diethylamino) dimethoxysilane, sec. -Butyl (dimethylamino) dimethoxysilane, sec. -Butyl (diethylamino) dimethoxysilane, tert. -Butyl (dimethylamino) dimethoxysilane, tert. Butyl (diethylamino) dimethoxysilane, isopropyl (dimethylamino) diethoxysilane, tert. Butyl (dimethylamino) diethoxysilane, isopropyl (dimethylamino) silane, tert. -Butyl (dimethylamino) silane etc. are mentioned.

  Also, methyl (4-dimethylaminophenyl) dimethoxysilane, methyl (4-diethylaminophenyl) dimethoxysilane, ethyl (4-dimethylaminophenyl) dimethoxysilane, ethyl (4-diethylaminophenyl) dimethoxysilane, vinyl (4-dimethylaminophenyl) ) Dimethoxysilane, vinyl (4-diethylaminophenyl) dimethoxysilane, n-propyl (4-dimethylaminophenyl) dimethoxysilane, n-propyl (4-diethylaminophenyl) dimethoxysilane, isopropyl (4-dimethylaminophenyl) dimethoxysilane, Isopropyl (4-diethylaminophenyl) dimethoxysilane, n-butyl (4-dimethylaminophenyl) dimethoxysilane, n-butyl (4-diethylaminophenyl) Silane, isobutyl (4-dimethylaminophenyl) dimethoxysilane, isobutyl (4-diethylamino-phenyl) dimethoxysilane, sec. -Butyl (4-dimethylaminophenyl) dimethoxysilane, sec. -Butyl (4-diethylaminophenyl) dimethoxysilane, tert. -Butyl (4-dimethylaminophenyl) dimethoxysilane, tert. -Butyl (4-diethylaminophenyl) dimethoxysilane and the like.

  Bis (4-dimethylaminophenyl) dimethoxysilane, bis (4-diethylaminophenyl) dimethoxysilane, bis (4-dimethylaminophenyl) diethoxysilane, bis (4-diethylaminophenyl) diethoxysilane, bis (4-dimethyl) Aminophenyl) silane, bis (4-diethylaminophenyl) silane and the like.

  Also methyl (dimethylboro) dimethoxysilane, methyl (diethylboro) dimethoxysilane, ethyl (dimethylboro) dimethoxysilane, ethyl (diethylboro) dimethoxysilane, vinyl (dimethylboro) dimethoxysilane, vinyl (diethylboro) dimethoxysilane, n-propyl (dimethylboro) dimethoxy Silane, n-propyl (diethylboro) dimethoxysilane, isopropyl (dimethylboro) dimethoxysilane, isopropyl (diethylboro) dimethoxysilane, n-butyl (dimethylboro) dimethoxysilane, n-butyl (diethylboro) dimethoxysilane, isobutyl (dimethylboro) dimethoxysilane, Isobutyl (diethylboro) dimethoxysilane, sec. -Butyl (dimethylboro) dimethoxysilane, sec. Butyl (diethylboro) dimethoxysilane, tert. -Butyl (dimethylboro) dimethoxysilane, tert. -Butyl (diethylboro) dimethoxysilane, methyl [bis (2,3,4,5,6-pentafluorophenyl) boro] dimethoxysilane, isopropyl (dimethylboro) diethoxysilane, tert. Butyl (dimethylboro) diethoxysilane, isopropyl (dimethylboro) silane, tert. -Butyl (dimethylboro) silane etc. are mentioned.

  Further, methyl (4-dimethylborophenyl) dimethoxysilane, methyl (4-diethylborophenyl) dimethoxysilane, ethyl (4-dimethylborophenyl) dimethoxysilane, ethyl (4-diethylborophenyl) dimethoxysilane, vinyl (4-dimethyl) Borophenyl) dimethoxysilane, vinyl (4-diethylborophenyl) dimethoxysilane, n-propyl (4-dimethylborophenyl) dimethoxysilane, n-propyl (4-diethylborophenyl) dimethoxysilane, isopropyl (4-dimethylborophenyl) ) Dimethoxysilane, isopropyl (4-diethylborophenyl) dimethoxysilane, n-butyl (4-dimethylborophenyl) dimethoxysilane, n-butyl (4-diethylborophenyl) dimethoxysilane, isobutyl Le (4-dimethylamino boro-phenyl) dimethoxysilane, isobutyl (4-diethyl-boro-phenyl) dimethoxysilane, sec. -Butyl (4-dimethylborophenyl) dimethoxysilane, sec. -Butyl (4-diethylborophenyl) dimethoxysilane, tert. -Butyl (4-dimethylborophenyl) dimethoxysilane, tert. -Butyl (4-diethylborophenyl) dimethoxysilane and the like.

  Bis (4-dimethylborophenyl) dimethoxysilane, bis (4-diethylborophenyl) dimethoxysilane, bis (4-dimethylborophenyl) diethoxysilane, bis (4-diethylborophenyl) diethoxysilane, bis (4 -Dimethylborophenyl) silane and bis (4-diethylborophenyl) silane.

  The Si-containing film-forming material of the present invention contains the silane compound represented by the above general formula (1), but other than silicon, carbon, oxygen, hydrogen, nitrogen, and boron can be used as the insulating film material. The amount of impurities is preferably less than 10 ppb and the water content is less than 50 ppm.

  Although the manufacturing method of the silane compound shown by the said General formula (1) is not specifically limited, For example, following General formula (7)

（式中、Ａは、前記に同じ。Ｘは、弗素原子、塩素原子、臭素原子、又は沃素原子を表す。）で示される有機ハロゲン化合物、
または、上記一般式（７）の有機ハロゲン化合物と、アルカリ金属、アルカリ土類金属、有機アルカリ金属、又は、有機アルカリ土類金属とを反応させて得た下記一般式（８）

(In the formula, A is the same as defined above; X represents a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom);
Alternatively, the following general formula (8) obtained by reacting the organic halogen compound of the general formula (7) with an alkali metal, alkaline earth metal, organic alkali metal, or organic alkaline earth metal

（式中、Ａ及びＸは、前記に同じ。Ｍは、アルカリ金属、又はアルカリ土類金属を表す。）で表される有機金属化合物と、下記一般式（９）

(Wherein, A and X are the same as above. M represents an alkali metal or an alkaline earth metal) and the following general formula (9)

（式中、Ｒ^１、Ｒ^２、Ｘ、ｑは、上記に同じ。ｒは、０乃至４の整数を表す。ｒ＋ｑは、４以下の整数を表す。）で示されるハロゲン化シラン、ハロゲン化アルコキシシラン又はテトラアルコキシシランとを反応させることにより、一般式（１）で表される有機シラン化合物を製造することができる。

(Wherein R ¹ , R ² , X, and q are the same as described above. R represents an integer of 0 to 4. r + q represents an integer of 4 or less.) By reacting with alkoxysilane or tetraalkoxysilane, the organosilane compound represented by the general formula (1) can be produced.

  The reaction solvent that can be used in the production of the silane compound represented by the general formula (1) is not particularly limited as long as it is used in the technical field. For example, n-pentane, i-pentane, saturated hydrocarbons such as n-hexane, cyclohexane, n-heptane and n-decane, unsaturated hydrocarbons such as toluene, xylene and decene-1, diethyl ether, diisopropyl ether, tert. -Ethers such as butyl methyl ether, dibutyl ether, cyclopentyl methyl ether, tetrahydrofuran, methanol, ethanol, isopropanol, n-butanol, tert. Alcohols such as butanol and 2-ethylhexanol can be used. Moreover, these mixed solvents can also be used. In particular, when ethers or alcohols are used, the silane compound represented by the general formula (1) having a specific molecular weight may be produced in a high yield.

  About the reaction temperature in the case of silane compound manufacture represented by General formula (1), it is the range which is usually used industrially -100-200 degreeC, Preferably, it is the range of -85-150 degreeC. It is preferable to carry out with. The pressure conditions for the reaction can be any of under pressure, normal pressure, and reduced pressure.

  About the purification method of the silane compound represented by the general formula (1) produced, the moisture content useful for use as an insulating film material is less than 50 ppm, impurities other than silicon, carbon, oxygen, hydrogen, nitrogen, boron, for example, In order to make the amount of metal impurities less than 10 ppb, a purification method such as atmospheric pressure or vacuum distillation or column separation using silica, alumina, or polymer gel can be used. At this time, these means may be used in combination as necessary. When moisture, elemental impurities other than silicon, carbon, oxygen, hydrogen, nitrogen, and boron, especially metal impurity residues, in the finally obtained silane compound represented by the general formula (1) are high, it is not suitable as an insulating film material. It will be something.

  In the production, it is preferable that other conditions follow the method in the organic synthesis and organometallic compound synthesis fields. 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 a dehydration operation in advance. Further, it is preferable to remove impurities such as metal residues and particles.

  The silane compound represented by the general formula (1) of the present invention is used as a Si-containing film forming material, and a Si-containing film can be produced using it as a raw material. The film formation method at this time is not limited, but is preferably performed by a chemical vapor deposition method, and particularly preferably by a plasma enhanced chemical vapor deposition (PECVD) method. This PECVD is generally used in the technical fields 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 plasma CVD 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. Also, it is within the scope of the present invention to simultaneously introduce an organic peroxide or an epoxy compound for the purpose of making the thin film porous.

  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, microwave plasma, or the like can be used. Various plasma generation sources such as an antenna type and a parallel plate type can be used. As PECVD conditions at this time, it is preferable to perform PECVD film formation with relatively low plasma power (W: voltage × current) as shown in the examples. Specifically, when the substrate size is from 2 inches to 12 inches, 1.0 W to 2000 W is preferable, and it is more preferable to perform in the range of 1.0 W to 1000 W.

  Further, a thin film with improved porosity or mechanical strength can be obtained by subjecting the above-mentioned Si-containing film to heat treatment, ultraviolet irradiation treatment, or electron beam treatment. The thin film obtained by this treatment is suitable as a low dielectric constant insulating material.

  All of the Si-containing films according to the present invention are suitable as low dielectric constant materials, and these can be used for semiconductor devices as insulating films. It is particularly suitable for the manufacture of ULSI using multilayer wiring.

  According to the present invention, the following remarkable effects are exhibited. That is, as a first effect of the present invention, by using the silane compound represented by the general formula (1) as the Si-containing film forming material, the low dielectric constant and the low dielectric constant material in the semiconductor device interlayer insulating film can be obtained. A material with high mechanical strength can be provided. Moreover, in this invention, the silane compound represented by General formula (1) useful as a PECVD method interlayer insulation film material can be efficiently manufactured with high purity.

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

Example 1 [Production of organometallic compound represented by general formula (8)]
Under a nitrogen stream, 26.7 g (2.20 mol) of metallic magnesium and 0.53 L of dry tetrahydrofuran were charged into a 1 L four-necked flask equipped with a dropping funnel and a stirrer, and cooled to 0 ° C. While stirring, 187 g (1.00 mol) of 4-bromoanisole was added dropwise over 5 hours and reacted at room temperature for 3 hours to obtain a tetrahydrofuran solution of 4-methoxyphenylmagnesium bromide.

[Production of organosilane compound represented by general formula (1)]
Under a nitrogen stream, 130 g (0.952 mol) of methyltrimethoxylane and 52.0 ml of dry tetrahydrofuran were charged into a 2 L four-necked flask equipped with a dropping funnel and a stirrer and cooled to 0 ° C. While stirring this, 1.00 mol of the tetrahydrofuran solution of 4-methoxyphenylmagnesium bromide prepared above was added dropwise over 1 hour and reacted at room temperature for 4 hours. After completion of the reaction, the by-product magnesium methoxide residue was removed by filtration, and the obtained filtrate was distilled under reduced pressure to obtain 106 g (0.501 mol) of methyl (4-methoxyphenyl) dimethoxysilane as the target product. The yield was 52.6%.

The results of analyzing the isolated methyl (4-methoxyphenyl) dimethoxysilane by ¹ H-NMR, ¹³ C-NMR, and GC-MS were as follows.

¹ H-NMR; δ 0.33 ppm (s, 3 H, C H ₃ —Si), δ 3.55 ppm (s, 6 H , 2 C H ₃ —O—Si), δ 3.81 ppm (s, 3 H, C H ₃ —O) -Ph), [delta] 6.93-6.94 ppm (m, 2H, Ph- H ), [delta] 7.55-7.56 ppm (m, 2H, Ph- H ),
¹³ C-NMR; δ 4.8 ppm ( C H ₃ —Si), 50.7 ppm ( C H ₃ —O—Si), 55.2 ppms ( C H ₃ —O—Ph), δ 113.9 ppm (Ph), δ 125 0.0 ppm (Ph), δ 135.8 ppm (Ph), δ 161.5 ppm (Ph)
_{GC-MS; Mw = 212,} C 10 H 16 О 3 Si.

In addition, the moisture and metal residue content in 100 g of the obtained methyl (4-methoxyphenyl) dimethoxysilane was measured using a Karl Fischer moisture meter and ICP-MS (high frequency plasma emission-mass analyzer, manufactured by Yokogawa Analytical Systems, Inc. The results measured by the name “HP4500”) are H ₂ O = 5 ppm, Li <10 ppb, Na <10 ppb, K <10 ppb, Mg <10 ppb, Ba <10 ppb, Sr <10 ppb, Cr <10 ppb, Ag <10 ppb, Cu. <10 ppb, Zn <10 ppb, Cd <10 ppb, Fe <10 ppb, Mn <10 ppb, Co <10 ppb, Ni <10 ppb, Ti <10 ppb, Zr <10 ppb, Al <10 ppb, Pb <10 ppb, Sn <10 ppb, W <10 ppb As an insulating film material It was useful.

Claims (14)

The following general formula (1)

(In the formula, A represents a group containing at least one selected from the group consisting of an oxygen atom, a boron atom, and a nitrogen atom, and R ¹ and R ² represent a hydrogen atom or a hydrocarbon group. 1 represents an integer of 1 to 4, and q represents an integer of 0 to 3. p + q is 1 to 4.) A Si-containing film-forming material comprising: A of the silane compound represented by the general formula (1) is represented by the following general formula (2)

(Wherein R ³ represents a hydrocarbon group, R ⁴ represents a hydrocarbon residue, x is the number of OR ³ substituted for R ⁴ and is an integer of 1 or more). The Si-containing film forming material according to claim 1, wherein: A of the silane compound represented by the general formula (1) is represented by the following general formula (3)

(Wherein R ⁵ represents a hydrocarbon residue) or the following general formula (4)

(Wherein R ⁵ represents a hydrocarbon group, R ⁶ represents a hydrocarbon residue, and y represents the number of NR ⁵ ₂ substituted for R ⁶ and is an integer of 1 or more). The Si-containing film forming material according to claim 1, wherein the Si-containing film forming material is provided. A of the silane compound represented by the general formula (1) is represented by the following general formula (5).

(Wherein R ⁷ represents a hydrocarbon residue) or the following general formula (6)

(Wherein R ⁷ represents a hydrocarbon group, R ⁸ represents a hydrocarbon residue, z is the number of BR ⁷ ₂ substituted for R ⁸ and is an integer of 1 or more). The Si-containing film forming material according to claim 1, wherein the Si-containing film forming material is provided. The Si-containing film forming material according to any one of claims 2 to ⁴ , wherein R ⁴ , R ⁶ , or R ⁸ is an aromatic group. The Si-containing film forming material according to claim 1, wherein the silane compound represented by the general formula (1) has a molecular weight of less than 1,000. The Si-containing film formation according to any one of claims 1 to 6, wherein the amount of impurities other than silicon, carbon, oxygen, hydrogen, nitrogen and boron is less than 10 ppb and the water content is less than 50 ppm. material. A method for producing a Si-containing film, wherein the Si-containing film forming material according to claim 1 is used as a raw material. The method according to claim 8, wherein film formation is performed by chemical vapor deposition. The method according to claim 9, wherein the chemical vapor deposition method is a plasma enhanced chemical vapor deposition method. A Si-containing film obtained by the production method according to claim 8. A method for producing a Si-containing film, wherein the Si-containing film according to claim 11 is subjected to heat treatment, ultraviolet irradiation treatment, or electron beam treatment. A Si-containing film obtained by the production method according to claim 12. 14. A semiconductor device using the film according to claim 11 as an insulating film.